Keratin dyeing compounds, keratin dyeing compositions containing them, and use thereof

ABSTRACT

Bicyclic 5-5 heteroaromatic compounds having a ring junction nitrogen and incorporating thia or oxa heteroatoms heteroatoms. Compositions for the oxidative dyeing of keratin fibers, comprising a medium suitable for dyeing and one or more bicyclic 5-5 heteroaromatic compounds having a ring junction nitrogen and incorporating thia or oxa heteroatoms heteroatoms. A method for oxidative dyeing of keratin fibers, comprising applying such compositions in the presence of an oxidizing agent, for a period sufficient to develop the desired coloration.

CROSS REFERENCE TO RELATED APPLICATION

The application claims the benefit of provisional application No.60/544,934 filed Feb. 13, 2004 (Case 9530P).

FIELD OF THE INVENTION

This invention relates to bicyclic 5-5 heteroaromatic compounds having aring junction nitrogen and incorporating thia or oxa heteroatoms,compositions for the oxidative dyeing of keratin fibers (preferablyhair) comprising such compounds, and use thereof.

BACKGROUND OF THE INVENTION

The most extensively used method currently employed to color hair is byan oxidative process that utilizes one or more oxidative hair coloringagents in combination with one or more oxidizing agents.

Commonly, a peroxy oxidizing agent is used in combination with one ormore developers or couplers, generally small molecules capable ofdiffusing into hair. In this procedure, a peroxide material, such ashydrogen peroxide, activates the developers so that they react with thecouplers to form larger sized compounds in the hair shaft to give avariety of shades and colors.

A wide variety of developers and couplers have been employed in suchoxidative hair coloring systems and compositions. However, there stillexists a need for additional keratin dyeing compounds that can act asboth developers and couplers that safely provide color benefits.

SUMMARY OF THE INVENTION

This invention relates to bicyclic 5-5 heteroaromatic compounds having aring junction nitrogen and incorporating thia or oxa heteroatomsheteroatoms according to the formulas defined herein. This inventionalso relates to a composition for the oxidative dyeing of keratinfibers, comprising a medium suitable for dyeing and one or more bicyclic5-5 heteroaromatic compounds having a ring junction nitrogen andincorporating thia or oxa heteroatoms heteroatoms. This inventionfurther relates to a method for oxidative dyeing of keratin fibers,comprising applying such compositions in the presence of an oxidizingagent, for a period sufficient to develop the desired coloration. Thekeratin dyeing compounds of the present invention can act as a developerand/or a coupler.

It is to be understood that within the scope of this invention, numerouspotentially and actually tautomeric compounds are involved. Thus, forexample, 2-mercaptopyridine (I) exists under known conditions in thepyridine-2-thione tautomer form (II):

It is to be understood that when this development refers to a particularstructure, all of the reasonable additional tautomeric structures areincluded. In the art, tautomeric structures are frequently representedby one single structure and the present invention follows this generalpractice.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims that particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

The present invention relates to bicyclic 5-5 heteroaromatic compoundshaving a ring junction nitrogen and incorporating thia or oxaheteroatoms. The compounds of the present invention can act as bothdevelopers and/or couplers that safely provide color benefits.

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. Thecompounds/compositions and methods/processes of the present inventioncan comprise, consist of, and consist essentially of the essentialelements and limitations of the invention described herein, as well asany of the additional or optional ingredients, components, steps, orlimitations described herein.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified. The term “weight percent” may be denoted as “wt. %” herein.

Except as otherwise noted, all amounts including part, percentages, andproportions are understood to be modified by the word “about”, andamounts are not intended to indicate significant digits. Except asotherwise noted, the articles “a”, “an”, and “the” mean “one or more”.

As used herein, the term “keratin” refers to a scleroprotein found inepidermal tissues and modified into hard structures such as horns, hair,and nails. Thus, “keratinous fibers” refers to those found in hair, skinand nails and various animal body parts such as horns, hooves andfeathers.

As used herein, the term “hair” refers to keratinous fibers on a living,e.g. a person, or non-living body, e.g. in a wig, hairpiece, or otheraggregation of non-living keratinous fibers. Mammalian, preferablyhuman, hair is a preferred. Notably, hair, wool, fur, and otherkeratinous fibers are suitable substrates for coloring by the compoundsand compositions described herein.

As used herein, the term “keratin dyeing compounds” refers to compoundsthat may be used in the composition to act as developers, couplers, orboth, in order to provide color to ketatinous fibers.

As used herein, the term “keratin dyeing composition” refers to thecomposition containing one or more keratin dyeing compounds, includingthe compounds described herein.

As used herein, “cosmetically acceptable” means that ingredients whichthe term describes are suitable for use in contact with the skin or hairof humans and lower animals without undue toxicity, incompatibility,instability, irritation, allergic response, and the like.

Keratin Dyeing Compounds

The inventive compounds are bicyclic 5-5 heteroaromatic compounds havinga ring junction nitrogen according to the following formulas:

-   -   wherein Y is selected from the group consisting of S and O;    -   wherein R¹, R², R⁴, R⁵, and R⁶ are the same or different and are        selected from the group consisting of:    -   (a) C-linked monovalent substituents selected from the group        consisting of:    -   (i) substituted or unsubstituted, straight or branched, alkyl,        mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems,        -   (ii) substituted or unsubstituted, mono- or poly-cyclic            aliphatic, aryl, or heterocyclic systems, and        -   (iii) substituted or unsubstituted, mono-, poly-, or            per-fluoro alkyl systems; wherein said systems of (i), (ii)            and (iii) comprise from about 1 to about 10 carbon atoms and            from about 0 to about 5 heteroatoms selected from the group            consisting of O, S, N, P, and Si;        -   wherein substituents of the substituted systems of the            C-linked monovalent substituents are selected from the group            consisting of amino, hydroxyl, alkylamino (linear or            branched C1-C5), dialkylamino (linear or branched C1-C5),            hydroxyalkylamino (linear or branched C1-C5),            dihydroxyalkylamino (linear or branched C1-C5), arylamino or            substituted arylamino (substituents are halogen, C1-C5            alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5            alkylamino), heteroarylamino or substituted heteroarylamino            (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,            trifluoromethyl, amino, C1-C5 alkylamino), arylmethylamino            or substituted arylmethylamino (substituents are halogen,            C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5            alkylamino), and heteroarylmethylamino or substituted            heteroarylmethylamino (substituents are halogen, C1-C5            alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5            alkylamino),    -   (b) S-linked monovalent substituents selected from the group        consisting of SA¹, SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A²,        and SONA¹A²;    -   (c) O-linked monovalent substituents selected from the group        consisting of OA¹, and ONA¹A²;    -   (d) N-linked monovalent substituents selected from the group        consisting of NA¹A², (NA¹A²A³)⁺, NA¹OA², NA¹SA², NO₂, N═NA¹,        N═NOA¹, NA¹CN, and NA¹NA²A³;    -   (e) monovalent substituents selected from the group consisting        of COOA¹, CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A², CN, and X;    -   (f) fluoroalkyl monovalent substituents selected from the group        consisting of mono-, poly-, and per-fluoro alkyl systems        comprising from about 1 to about 12 carbon atoms and from about        0 to about 4 heteroatoms; and    -   (g) hydrogen        -   wherein A¹, A², and A³ are monovalent and are independently            selected from the group consisting of: H; substituted or            unsubstituted, straight or branched, alkyl, mono- or            poly-unsaturated alkyl, heteroalkyl, aliphatic,            heteroaliphatic, or heteroolefinic systems; substituted or            unsubstituted, mono- or poly-cyclic aliphatic, aryl, or            heterocyclic systems; and substituted or unsubstituted,            mono-, poly-, or per-fluoro alkyl systems, or A¹ and A²            together with nitrogen atom to which they are bound form a            ring; wherein said systems comprise from about 1 to about 10            carbon atoms and from about 0 to about 5 heteroatoms            selected from the group consisting of O, S, N, P, and Si;        -   wherein X is a halogen selected from the group consisting of            F, Cl, Br, and I.

In a preferred embodiment, R¹, R², R⁴, R⁵, and R⁶ are selected from thegroup consisting of a hydrogen atom; a halogen atom such as chlorine,bromine or fluorine; an amino substituent, a hydroxyl substituent; acyano substituent; a C₁-C₄ alkyl substituent; a trifluoromethylsubstituent, an alkylamino substituent (e.g., N,N-dimethylamino,N,N-diethylamino, N-methylamino, or N-ethylamino); a hydroxyalkylaminosubstituent (e.g., N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino or N,N-bis(hydroxypropyl)amino); anacetylamido substituent; a carboxyl substituent or its esters; an alkoxysubstituent (e.g., methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, phenoxyethoxy,p-chlorobenzyloxy or methoxyethylcarbamoylmethoxy); an alkoxyalkylsubstituent (e.g., methoxymethyl, methoxyethyl, methoxypropyl,ethoxymethyl, ethoxyethyl or ethoxypropyl); a carbamoyl substituent; analkylcarbamoyl substituent (e.g., methylcarbamoyl, ethylcarbamoyl,dimethylcarbamoyl, or diethylcarbamoyl); a hydroxyalkylcarbamoylsubstituent (e.g., 2-hydroxyethylcarbamoyl,bis(2-hdyroxyethyl)carbamoyl, hydroxymethylcarbamoyl,bis(hydroxymethyl)carbamoyl); an amido substituent; an alkylamidosubstituent (e.g., acetamido, propionamido, or butyramido); analkylcarbonyl substituent (e.g., acetyl, butyryl, or propionyl), analkoxycarbonyl substituent (e.g., methoxycarbonyl, ethoxycarbonyl, orpropoxycarbonyl); an aryloxy substituent (e.g., phenoxy,4-methoxyphenoxy, 4-nitrophenoxy, 4-cyanophenoxy,4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, 3-methylphenoxyor 1-naphthyloxy); an acyloxy substituent (e.g., acetoxy, propanoyloxy,benzolyloxy, 2,4-dichlorobenzolyloxy, ethoxyalkyloxy, pyruviloyloxy,cinnamoyloxy or myristoyloxy); an alkylthio substituent (e.g.,methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio,benzylthio, phenethylthio, 2-(diethylamino)ethylthio, ethoxyethylthio orphenoxyethylthio); an arylthio substituent (e.g., phenylthio,4-carboxyphenylthio, 2-ethoxy-5-tert-butylphenylthio,2-carboxyphenylthio or 4-methanesulfonylphenylthio); a heteroarylthiosubstituent (e.g., 5-phenyl-2,3,4,5-tetrazolyloxy or2-benzothiazolyloxy); a heteroaryloxy substituent (e.g.,5-phenyl-2,3,4,5-tetrazolyloxy or 2-benzothiazolyloxy); a 3-, 4-, 5-,6-, or 7-membered heterocycle having at least one nitrogen, oxygen orsulfur atom (e.g., pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, oxazolyl, imidazolyl, thiadiazolyl,pyrollidine, piperidine, morpholine, piperazine, indoline,hexahydroazepine, aziridine, and azetidine) and being optionallysubstituted; an aryl substituent (e.g., phenyl or naphthyl) which isoptionally substituted; a sulfonyl substituent; a sulfinyl substituent;a phosphonyl substituent; a sulfamoyl substituent; a siloxy substituent;an acyloxy substituent; a carbamoyloxy substituent; a sulphonamidesubstituent; an imide substituent; a ureido substituent; asulfamoylamino substituent; an alkoxycarbonylamino substituent; anaryloxycarbonylamino substituent; an aryloxycarbonyl substituent; and abenzenesulfonamido substituent.

If the compound of the present invention is utilized as a developer, atleast one of R¹, R⁴ or R⁶ is an amino group, with preferably at leastone of the remaining R¹, R², R⁴, R⁵, and R⁶ being selected fromsubstituents selected from the group consisting of Amino, hydroxyl, a3-, 4-, 5-, 6-, or 7-membered heterocycle having at least one nitrogen,oxygen or sulfur atom (e.g., pyridyl, quinolyl, morpholyl, furyl,tetrahydrofuryl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, imidazolyl,thiadiazolyl, pyrollidine, piperidine, morpholine, piperazine, indoline,hexahydroazepine, aziridine, and azetidine) and being optionallysubstituted, Alkylamino (linear, branched, or cyclic C1-C5),Dialkylamino (linear, branched, or cyclic C1-C5), Hydroxyalkylamino(linear, branched, or cyclic C1-C5), Dihydroxyalkylamino (linear,branched, or cyclic C1-C5), Arylamino or substituted arylamino(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, C1-C5 alkylamino), Heteroarylamino or substituted heteroarylamino(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, C1-C5 alkylamino), Arylmethylamino or substituted arylmethylamino(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, C1-C5 alkylamino), and Heteroarylmethylamino or substitutedheteroarylmethylamino (substituents are halogen, C1-C5 alkyl, C1-C5alkoxy, trifluoromethyl, amino, C1-C5 alkylamino).

If the compound of the present invention is utilized as a coupler,preferred substituents are selected from the group consisting of Amino,Hydroxyl, Alkylamino (linear or branched C1-C5), Hydroxyalkylamino(linear or branched C1-C5), Arylamino or substituted arylamino(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, C1-C5 alkylamino), Heteroarylamino or substituted heteroarylamino(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, C1-C5 alkylamino), Arylmethylamino or substituted arylmethylamino(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, C1-C5 alkylamino), and Heteroarylmethylamino or substitutedheteroarylmethylamino (substituents are halogen, C1-C5 alkyl, C1-C5alkoxy, trifluoromethyl, amino, C1-C5 alkylamino).

The developers and couplers of the present invention can alsoaccommodate nucleofugic leaving groups selected from the groupconsisting of hydrogen, chlorine, cyano, alkoxy, phenoxy,methylsulfonyoxy, pyridone and pyridazone.

In a preferred embodiment, the couplers of the present invention areutilized in compositions together with suitable 5-membered ringdevelopers chosen from the following classes: thiophenes, pyrroles,furans, pyrazoles, imidazoles, thiazoles, oxazoles, isothiazoles, orisoxazoles. In a more preferred embodiment, the couplers of the presentinvention are utilized in compositions together with with developersthat are pyrazoles. In an even more preferred embodiment, the couplersof the present invention are utilized in compositions together with thefollowing pyrazole developers: 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine and1-Hydroxyethyl-4,5-diaminopyrazole sulphate. Even more preferably, thecouplers of the present invention are utilized in compositions togetherwith 1-methyl-1H-pyrazole-4,5-diamine;1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and2-(4,5-diamino-1H-pyrazol-1-yl)ethanol. While not being bound to theory,such combinations enable the achievement of desired more hypsochromiccolors (e.g., yellow) relative to conventional combinations ofdevelopers and couplers.

In a further preferred embodiment, the couplers of the present inventionhave a computed apparent partition coefficient, Log D, at pH 10 ofbetween −2.5 and 3.5, preferably between −1.5 and 3.0, more preferablybetween −0.5 and 2.5. Log D takes into account the extent of ionisationand can be computed via ACD/Labs 6.0 software available from AdvancedChemistry Development Inc. Copyright© 1994-2002.

The inventive compounds may be substituted pyrrolo[2,1-b]thiazoles orpyrrolo[2,1-b]oxazoles, pyrrolo[5,1-b]thiazoles orpyrrolo[5,1-b]oxazoles, imidazo[5,1-b]thiazoles orimidazo[5,1-b]oxazoles, imidazo[2,1-b]thiazoles orimidazo[2,1-b]oxazoles, pyrrolo[2,1-b][1,3,4]thiadiazoles orpyrrolo[2,1-b][1,3,4]oxadiazoles, pyrrolo[1,2-d][1,2,4]thiadiazoles orpyrrolo[1,2-d][1,2,4]oxadiazoles, thiazolo[3,2-e][1,2,3]triazoles oroxazolo[3,2-e][1,2,3]triazoles, thiazolo[3,2-b][1,2,4]triazoles oroxazolo[3,2-b][1,2,4]triazoles, thiazolo[2,3-c][1,2,4]triazoles oroxazolo[2,3-c][1,2,4]triazoles, pyrazolo[5,1-b][1,3,4]thiadiazoles orpyrazolo[5,1-b][1,3,4]oxadiazoles, imidazo[5,1-b][1,3,4]thiadiazoles orimidazo[5,1-b][1,3,4]oxadiazoles, imidazo[2,1-b][1,3,4]thiadiazoles orimidazo[2,1-b][1,3,4]oxadiazoles, or one of the corresponding additionsalts with an acid.

Preferred developers and couplers include the following bicyclicheteroaromatic compounds having a ring junction nitrogen andincorporating thia or oxa heteroatoms:

(I) Pyrrolo[2,1-b]thiazoles and Pyrrolo[2,1-b]oxazoles

a. Preferred Developers

Preferred developers of formula I are selected from the group consistingof pyrrolo[2,1-b]thiazoles and pyrrolo[2,1-b]oxazoles according to thefollowing formulas:

-   -   wherein Y is selected from the group consisting of S and O;    -   wherein D² and D⁵ are each independently selected from the group        consisting of amino, hydroxyl, N,N-dimethylamino,        N,N-diethylamino, N-methylamino, N-ethylamino,        N-(hydroxyethyl)amino, N-hydroxymethylamino,        N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,        N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino,        N-phenyl, N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy,        methoxyethoxy, phenoxyethoxy, phenoxy, methylthio, ethylthio,        propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyl        and thiadiazolyl; and

wherein E¹, E², E⁴, E⁵ and E⁶ are each independently selected from thegroup consisting of hydrogen, chlorine, bromine, fluorine, amino,hydroxyl, cyano, methyl, ethyl, isopropyl, trifluoromethyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylaminoN,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino), carboxyl, methoxy, ethoxy, propyloxy,benzyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, amido, acetamido, propionamido, butyramido,acetyl, butyryl, propionyl, phenoxy, methylthio, ethylthio, propylthio,butylthio, pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl,thiadiazolyl, phenyl, sulfonyl, sulphonamido, and ureido.

Especially preferred developers of the present invention according toformulas Ia, Ib and Ic are selected from the group consisting ofpyrrolo[2,1-b]thiazole-5,6-diamine, 5-aminopyrrolo[2,1-b]thiazol-6-ol,pyrrolo[2,1-b]thiazol-7-amine, pyrrolo[2,1-b]thiazole-2,3-diamine,pyrrolo[2,1-b]thiazol-5-amine, 3-aminopyrrolo[2,1-b]thiazol-2-ol,pyrrolo[2,1-b]oxazole-5,6-diamine, 5-aminopyrrolo[2,1-b]oxazol-6-ol,pyrrolo[2,1-b]oxazol-7-amine, pyrrolo[2,1-b]oxazole-2,3-diamine,pyrrolo[2,1-b]oxazol-5-amine, and 3-aminopyrrolo[2,1-b]oxazol-2-ol.

b. Preferred Couplers

Preferred couplers of formula I are selected from the group consistingof pyrrolo[2,1-b]thiazoles and pyrrolo[2,1-b]oxazoles according to thefollowing formulas:

-   -   wherein Y, D², D⁵, E¹, E², E⁴, E⁵ and E⁶ are as defined above.

Especially preferred couplers of the present invention according toformulas Id, Ie, and If are selected from the group consisting ofpyrrolo[2,1-b]thiazol-6-amine, pyrrolo[2,1-b]thiazol-6-ol,6-methylpyrrolo[2,1-b]thiazole, pyrrolo[2,1-b]thiazole-3,6-diamine,pyrrolo[2,1-b]thiazole-6,7-diamine, pyrrolo[2,1-b]thiazol-2-amine,pyrrolo[2,1-b]thiazol-2-ol, pyrrolo[2,1-b]oxazol-6-amine,pyrrolo[2,1-b]oxazol-6-ol, 6-methylpyrrolo[2,1-b]oxazole,pyrrolo[2,1-b]oxazole-3,6-diamine, pyrrolo[2,1-b]oxazole-6,7-diamine,pyrrolo[2,1-b]oxazol-2-amine, and pyrrolo[2,1-b]oxazol-2-ol.

(II) Pyrazolor5,1-b]thiazoles and Pyrazolo [5,1-b]oxazoles

a. Preferred Developers

Preferred developers of formula II are selected from the groupconsisting of pyrazolo[5,1-b]thiazoles and pyrazolo[5,1-b]oxazolesaccording to the following formulas:

-   -   wherein Y, D², E¹, E², E⁴, and E⁵ are as defined above.

Especially preferred developers of the present invention according toformulas IIa and IIb are selected from the group consisting ofpyrazolo[5,1-b]thiazol-7-amine,6-methyl-pyrazolo-[5,1-b]thiazole-7-amine,pyrazolo[5,1-b]thiazole-6,7-diamine, 7-aminopyrazolo[5,1-b]thiazol-6-ol,pyrazolo[5,1-b]thiazole-2,3-diamine, 3-aminopyrazolo[5,1-b]thiazol-2-ol,pyrazolo[5,1-b]oxazol-7-amine, pyrazolo[5,1-b]oxazole-6,7-diamine,7-aminopyrazolo[5,1-b]oxazol-6-ol, pyrazolo[5,1-b]oxazole-2,3-diamine,and 3-aminopyrazolo[5,1-b]oxazol-2-ol.

b. Preferred Couplers

Preferred couplers of formula II are selected from the group consistingof pyrazolo[5,1-b]thiazoles and pyrazolo[5,1-b]oxazoles according to thefollowing formulas:

-   -   wherein Y, D², E¹, E², E⁴, and E⁵ are as defined above.

Especially preferred couplers of the present invention according toformulas IIc and IId are selected from the group consisting ofpyrazolo[5,1-b]thiazol-6-amine, pyrazolo[5,1-b]thiazol-6-ol,pyrazolo[5,1-b]thiazole-3,6-diamine,pyrazolo[5,1-b]thiazole-6,7-diamine, pyrazolo[5,1-b]thiazol-2-amine,pyrazolo[5,1-b]thiazol-2-ol, pyrazolo[5,1-b]oxazol-6-amine,pyrazolo[5,1-b]oxazol-6-ol, pyrazolo[5,1-b]oxazole-3,6-diamine,pyrazolo[5,1-b]oxazole-6,7-diamine, pyrazolo[5,1-b]oxazol-2-amine, andpyrazolo[5,1-b]oxazol-2-ol.

(III) Imidazo[5,1-b]thiazoles and Imidazo[5,1-b]oxazoles

a. Preferred Developers

Preferred developers of formula III are selected from the groupconsisting of imidazo[5,1-b]thiazoles and imidazo[5,1-b]oxazolesaccording to the following formulas:

-   -   wherein Y, D², E¹, E², E⁴, and E⁶ are as defined above.

Especially preferred developers of the present invention according toformulas IIIa, IIIb, and IIIc are selected from the group consisting ofimidazo[5,1-b]thiazole-7-amine, imidazo[5,1-b]thiazole-5,7-diamine,imidazo[5,1-b]thiazole-3,5,7-triamine,5-aminoimidazo[5,1-b]thiazole-7-ol, imidazo[5,1-b]thiazole-7-amine,imidazo[5,1-b]thiazole-2,3-diamine, imidazo[5,1-b]thiazole-5-amine,3-aminoimidazo[5,1-b]thiazole-2-ol, imidazo[5,1-b]oxazole-5,7-diamine,5-aminoimidazo[5,1-b]oxazole-7-ol, imidazo[5,1-b]oxazole-7-amine,2-methyl-imidazo[5,1-b]oxazole-7-amine,imidazo[5,1-b]oxazole-2,3-diamine, imidazo[5,1-b]oxazole-5-amine, and3-aminoimidazo[5,1-b]oxazole-2-ol.

b. Preferred Couplers

Preferred couplers of formula III are selected from the group consistingof imidazo[5,1-b]thiazoles and imidazo[5,1-b]oxazoles according to thefollowing formulas:

-   -   wherein Y, D², E¹, E², E⁴, and E⁶ are as defined above.

Especially preferred couplers of the present invention according toformulas IIId, IIIe, and IIIf are selected from the group consisting ofimidazo[5,1-b]thiazole-3,7-diamine, imidazo[5,1-b]thiazole-3,7-diol,imidazo[5,1-b]thiazole-3,5-diamine, imidazo[5,1-b]thiazole-2,7-diamine,imidazo[5,1-b]thiazole-2-amine, imidazo[5,1-b]thiazole-2-ol,imidazo[5,1-b]oxazole-3,7-diamine, imidazo[5,1-b]oxazole-3,7-diol,imidazo[5,1-b]oxazole-3,5-diamine, imidazo[5,1-b]oxazole-2,7-diamine,imidazo[5,1-b]oxazole-2-amine, and imidazo[5,1-b]oxazole-2-ol.

(IV) Imidazo[2, 1-b]thiazoles and Imidazo[2,1-b]oxazoles

a. Preferred Developers

Preferred developers of formula IV are selected from the groupconsisting of imidazo[2,1-b]thiazoles and imidazo[2,1-b]oxazolesaccording to the following formulas:

-   -   wherein Y, D², D⁵, E¹, E², E⁵, and E⁶ are as defined above.

Especially preferred developers of the present invention according toformulas IVa and IVb are selected from the group consisting ofimidazo[2,1-b]thiazole-5-amine, imidazo[2,1-b]thiazole-5,6-diamine,5-amino imidazo[2,1-b]thiazole-6-ol, imidazo[2,1-b]thiazole-2,3-diamine,3-amino imidazo[2,1-b]thiazole-2-ol, imidazo[2,1-b]oxazole-5-amine,imidazo[2,1-b]oxazole-5,6-diamine, 5-amino imidazo[2,1-b]oxazole-6-ol,imidazo[2,1-b]oxazole-2,3-diamine, and 3-aminoimidazo[2,1-b]oxazole-2-ol.

b. Preferred Couplers

Preferred couplers of formula IV are selected from the group consistingof imidazo[2,1-b]thiazoles and imidazo[2,1-b]oxazoles according to thefollowing formulas:

-   -   wherein Y, D², D⁵, E¹, E², E⁵, and E⁶ are as defined above.

Especially preferred couplers of the present invention according toformulas IVc and IVd are selected from the group consisting ofimidazo[2,1-b]thiazole-6-amine, imidazo[2,1-b]thiazole-6-ol,imidazo[2,1-b]thiazole-3,6-diamine, imidazo[2,1-b]thiazole-5,6-diamine,imidazo[2,1-b]thiazole-2-amine, imidazo[2,1-b]thiazole-2-ol,imidazo[2,1-b]oxazole-6-amine, imidazo[2,1-b]oxazole-6-ol,imidazo[2,1-b]oxazole-3,6-diamine, imidazo[2,1-b]oxazole-5,6-diamine,imidazo[2,1-b]oxazole-2-amine, and imidazo[2,1-b]oxazole-2-ol.

(V) Pyrrolo[2,1-b][1,3,4]thiadiazoles andPyrrolo[2,1-b][1,3,4]oxadiazoles

a. Preferred Developers

Preferred developers of formula V are selected from the group consistingof pyrrolo[2,1-b][1,3,4]thiadiazoles andpyrrolo[2,1-b][1,3,4]oxadiazoles according to the following formulas:

-   -   wherein Y, D⁵, E², E⁴, E⁵, and E⁶ are as defined above.

Especially preferred developers of the present invention according toformulas Va and Vb are selected from the group consisting ofpyrrolo[2,1-b][1,3,4]thiadiazole-7-amine,pyrrolo[2,1-b][1,3,4]thiadiazole-5-amine,pyrrolo[2,1-b][1,3,4]thiadiazole-5,6-diamine,5-aminopyrrolo[2,1-b][1,3,4]thiadiazole-6-ol,pyrrolo[2,1-b][1,3,4]thiadiazole-6,7-diamine,5-aminopyrrolo[2,1-b][1,3,4]thiadiazole-2-ol,pyrrolo[2,1-b][1,3,4]oxadiazole-7-amine,pyrrolo[2,1-b][1,3,4]oxadiazole-5-amine,pyrrolo[2,1-b][1,3,4]oxadiazole-5,6-diamine,5-aminopyrrolo[2,1-b][1,3,4]oxadiazole-6-ol,pyrrolo[2,1-b][1,3,4]oxadiazole-6,7-diamine, and5-aminopyrrolo[2,1-b][1,3,4]oxadiazole-2-ol.

b. Preferred Couplers

Preferred couplers of formula V are selected from the group consistingof pyrrolo[2,1-b][1,3,4]thiadiazoles andpyrrolo[2,1-b][1,3,4]oxadiazoles according to the following formulas:

-   -   wherein Y, D⁵, E², E⁴, E⁵, and E⁶ are as defined above.

Especially preferred couplers of the present invention according toformulas Vc and Vd are selected from the group consisting ofpyrazolo[5,1-b]thiazol-6-amine, pyrazolo[5,1-b]thiazol-6-ol,pyrazolo[5,1-b]thiazole-2,6-diamine, pyrazolo[5,1-b]thiazole-2,6-diol,pyrazolo[5,1-b]thiazol-2,7-diol, pyrazolo[5,1-b]oxazol-6-amine,pyrazolo[5,1-b]oxazol-6-ol, pyrazolo[5,1-b]oxazole-2,6-diamine,pyrazolo[5,1-b]oxazole-2,6-diol, and pyrazolo[5,1-b]oxazol-2,7-diol.

(VI) Pyrrolo[1,2-d][1,2,4]thiadiazoles andPyrrolo[1,2-d][1,2,4]oxadiazoles

a. Preferred Developers

Preferred developers of formula VI are selected from the groupconsisting of pyrrolo[1,2-d][1,2,4]thiadiazoles andpyrrolo[1,2-d][1,2,4]oxadiazoles according to the following formulas:

-   -   wherein Y, D⁵, E¹, E⁴, E⁵, and E⁶ are as defined above.

Especially preferred developers of the present invention according toformulas VIa, VIb, and VIc are selected from the group consisting ofpyrrolo[1,2-d][1,2,4]thiadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]thiadiazole-3,5,6-triamine,5-aminopyrrolo[1,2-d][1,2,4]thiadiazole-6-ol,pyrrolo[1,2-d][1,2,4]thiadiazole-pyrrolo[1,2-d][1,2,4]thiadiazole-5-amine,pyrrolo[1,2-d][1,2,4]thiadiazole-6,7-diamine-,5-aminopyrrolo[1,2-d][1,2,4]thiadiazole-7-ol,pyrrolo[1,2-d][1,2,4]thiadiazole-3,6,7-triol,1,2-d][1,2,4]oxadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]oxadiazole-3,5,6-triamine,5-aminopyrrolo[1,2-d][1,2,4]oxadiazole-6-ol,pyrrolo[1,2-d][1,2,4]oxadiazole-7-amine,pyrrolo[1,2-d][1,2,4]oxadiazole-5-amine,pyrrolo[1,2-d][1,2,4]oxadiazole-6,7-diamine,5-aminopyrrolo[1,2-d][1,2,4]oxadiazole-7-ol, andpyrrolo[1,2-d][1,2,4]oxadiazole-3,6,7-triol.

b. Preferred Couplers

Preferred couplers of formula VI are selected from the group consistingof pyrrolo[1,2-d][1,2,4]thiadiazoles andpyrrolo[1,2-d][1,2,4]oxadiazoles according to the following formulas:

-   -   wherein Y, D⁵, E¹, E⁴, E⁵, and E⁶ are as defined above.

Especially preferred couplers of the present invention according toformulas VId, VIe and VIf are selected from the group consisting ofpyrrolo[1,2-d][1,2,4]thiadiazole-6,7-diamine,pyrrolo[1,2-d][1,2,4]thiadiazole-6,7-diol,pyrrolo[1,2-d][1,2,4]thiadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]thiadiazole-6-amine,pyrrolo[1,2-d][1,2,4]thiadiazole-6-ol,pyrrolo[1,2-d][1,2,4]oxadiazole-6,7-diamine,pyrrolo[1,2-d][1,2,4]oxadiazole-6,7-diol,pyrrolo[1,2-d][1,2,4]oxadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]oxadiazole-6-amine, andpyrrolo[1,2-d][1,2,4]oxadiazole-6-ol, 2-ol.

(VII) Thiazolo[3,2-e][1,2,3]triazoles and Oxazolo[3,2-e][1,2,3]triazoles

a. Preferred Developers

Preferred developers of formula VII are selected from the groupconsisting of thiazolo[3,2-e][1,2,3]triazoles andoxazolo[3,2-e][1,2,3]triazoles relating according to the followingformulas:

-   -   wherein Y, D¹, D², and D⁴ are as defined above.

Especially preferred developers of the present invention according toformulas VIIa and VIIb are selected from the group consisting ofthiazolo[3,2-e][1,2,3]triazole-7-amine,thiazolo[3,2-e][1,2,3]triazole-2,3,7-triamine,7-aminothiazolo[3,2-e][1,2,3]triazole-2,3-diol,3,7-diaminothiazolo[3,2-e][1,2,3]triazole-2-ol,2,3-diaminothiazolo[3,2-e][1,2,3]triazole-7-ol,3,7-triaminothiazolo[3,2-e][1,2,3]triazole-2-ol,oxazolo[3,2-e][1,2,3]triazole-7-amine,oxazolo[3,2-e][1,2,3]triazole-2,3,7-triamine,7-aminooxazolo[3,2-e][1,2,3]triazole-2,3-diol,3,7-diaminooxazolo[3,2-e][1,2,3]triazole-2-ol,2,3-diaminooxazolo[3,2-e][1,2,3]triazole-7-ol, and3,7-triaminooxazolo[3,2-e][1,2,3]triazole-2-ol.

c. Preferred Couplers

Preferred couplers of formula VII are selected from the group consistingof thiazolo[3,2-e][1,2,3]triazoles and oxazolo[3,2-e][1,2,3]triazolesaccording to the following formulas:

-   -   wherein Y, D¹, D², and D⁴ are as defined above.

Especially preferred couplers of the present invention according toformulas VIIc and VIId are selected from the group consisting ofthiazolo[3,2-e][1,2,3]triazole-2,3-diamine,thiazolo[3,2-e][1,2,3]triazole-2,3-diol,thiazolo[3,2-e][1,2,3]triazole-2,7-diamine,2-aminothiazolo[3,2-e][1,2,3]triazole-7-ol,7-aminothiazolo[3,2-e][1,2,3]triazole-2-ol,oxazolo[3,2-e][1,2,3]triazole-2,3-diamine,oxazolo[3,2-e][1,2,3]triazole-2,3-diol,oxazolo[3,2-e][1,2,3]triazole-2,7-diamine,2-aminooxazolo[3,2-e][1,2,3]triazole-7-ol, and7-aminooxazolo[3,2-e][1,2,3]triazole-2-ol.

(VIII) Thiazolo[3,2-b][1,2,4]triazoles andOxazolo[3,2-b][1,2,4]triazoles

a. Preferred Developers

Preferred developers of formula VIII are selected from the groupconsisting of thiazolo[3,2-b][1,2,4]triazoles andoxazolo[3,2-b][1,2,4]triazoles according to the following formula:

-   -   wherein Y, D² and D⁵ are as defined above.

Especially preferred developers of the present invention according toformula VIIIa are selected from the group consisting ofthiazolo[3,2-b][1,2,4]triazole-2,3,6-triamine,3-aminothiazolo[3,2-b][1,2,4]triazole-2,6-diol,2,3-diaminothiazolo[3,2-b][1,2,4]triazole-6-ol,oxazolo[3,2-b][1,2,4]triazole-2,3,6-triamine,3-aminooxazolo[3,2-b][1,2,4]triazole-2,6-diol, and2,3-diaminooxazolo[3,2-b][1,2,4]triazole-6-ol.

b. Preferred Couplers

Preferred couplers of formula VIII are selected from the groupconsisting of thiazolo[3,2-b][1,2,4]triazoles andoxazolo[3,2-b][1,2,4]triazoles according to the following formula:

-   -   wherein Y, D² and D⁵ are as defined above.

Especially preferred couplers of the present invention according toformula VIIIb are selected from the group consisting ofthiazolo[3,2-b][1,2,4]triazole-2,6-diamine,thiazolo[3,2-b][1,2,4]triazole-2,6-diol,2-aminothiazolo[3,2-b][1,2,4]triazole-6-ol,6-aminothiazolo[3,2-b][1,2,4]triazole-2-ol,oxazolo[3,2-b][1,2,4]triazole-2,6-diamine,oxazolo[3,2-b][1,2,4]triazole-2,6-diol,2-aminooxazolo[3,2-b][1,2,4]triazole-6-ol, and6-aminooxazolo[3,2-b][1,2,4]triazole-2-ol.

(IX) Thiazolo[2,3-c][1,2,4]triazoles and Oxazolo[2,3-c][1,2,4]triazoles

a. Preferred Developers

Preferred developers of formula IX are selected from the groupconsisting of thiazolo[2,3-c][1,2,4]triazoles andoxazolo[2,3-c][1,2,4]triazoles according to the following formulas:

-   -   wherein Y, D¹, D², and D⁶ are as defined above.

Especially preferred developers of the present invention according toformulas IXa and IXb are selected from the group consisting ofthiazolo[2,3-c][1,2,4]triazole-5-amine,thiazolo[2,3-c][1,2,4]triazole-2,3,5-triamine,3-aminothiazolo[2,3-c][1,2,4]triazole-2,5-diol,2,5-diaminothiazolo[2,3-c][1,2,4]triazole-3-ol,5-aminothiazolo[2,3-c][1,2,4]triazole-2,3-diol,3,5-diaminothiazolo[2,3-c][1,2,4]triazole-2-ol,oxazolo[2,3-c][1,2,4]triazole-5-amine,oxazolo[2,3-c][1,2,4]triazole-2,3,5-triamine,3-aminooxazolo[2,3-c][1,2,4]triazole-2,5-diol,2,5-diaminooxazolo[2,3-c][1,2,4]triazole-3-ol,5-aminooxazolo[2,3-c][1,2,4]triazole-2,3-diol, and3,5-diaminooxazolo[2,3-c][1,2,4]triazole-2-ol.

b. Preferred Couplers

Preferred couplers of formula IX are selected from the group consistingof thiazolo[2,3-c][1,2,4]triazoles and oxazolo[2,3-c][1,2,4]triazolesaccording to the following formulas:

-   -   wherein Y, D¹, D², and D⁶ are as defined above.

Especially preferred couplers of the present invention according toformulas IXc and IXd are selected from the group consisting ofthiazolo[2,3-c][1,2,4]triazole-2,3-diamine,thiazolo[2,3-c][1,2,4]triazole-2,3-diol,thiazolo[2,3-c][1,2,4]triazole-2,5-diol,thiazolo[2,3-c][1,2,4]triazole-2,5-diamine,oxazolo[2,3-c][1,2,4]triazole-2,3-diamine,oxazolo[2,3-c][1,2,4]triazole-2,3-diol,oxazolo[2,3-c][1,2,4]triazole-2,5-diol, andoxazolo[2,3-c][1,2,4]triazole-2,5-diamine.

(X) Pyrazolo[5,1-b][1,3,4]thiadiazoles andPyrazolo[5,1-b][1,3,4]oxadiazoles

a. Preferred Developers

Preferred developers of formula X are selected from the group consistingof pyrazolo[5,1-b][1,3,4]thiadiazoles andpyrazolo[5,1-b][1,3,4]oxadiazoles according to the following formula:

-   -   wherein Y, D² and D⁵ are as defined above.

Especially preferred developers of the present invention according toformula Xa are selected from the group consisting ofpyrazolo[5,1-b][1,3,4]thiadiazole-7-amine,pyrazolo[5,1-b][1,3,4]thiadiazole-2,6,7-triamine,7-aminopyrazolo[5,1-b][1,3,4]thiadiazole-2,6-diol,6,7-diaminopyrazolo[5,1-b][1,3,4]thiadiazole-2-ol,2,7-diaminopyrazolo[5,1-b][1,3,4]thiadiazole-6-ol,pyrazolo[5,1-b][1,3,4]oxadiazole-7-amine,pyrazolo[5,1-b][1,3,4]oxadiazole-2,6,7-triamine,7-aminopyrazolo[5,1-b][1,3,4]oxadiazole-2,6-diol,6,7-diaminopyrazolo[5,1-b][1,3,4]oxadiazole-2-ol, and2,7-diaminopyrazolo[5,1-b][1,3,4]oxadiazole-6-ol.

b. Preferred Couplers

Preferred couplers of formula X are selected from the group consistingof pyrazolo[5,1-b][1,3,4]thiadiazoles andpyrazolo[5,1-b][1,3,4]oxadiazoles according to the following formula:

-   -   wherein Y, D² and D⁵ are as defined above.

Especially preferred couplers of the present invention according toformula Xb are selected from the group consisting ofpyrazolo[5,1-b][1,3,4]thiadiazole-2,6-diamine,pyrazolo[5,1-b][1,3,4]thiadiazole-2,6-diol,2-aminopyrazolo[5,1-b][1,3,4]thiadiazole-6-ol,6-aminopyrazolo[5,1-b][1,3,4]thiadiazole-2-ol,pyrazolo[5,1-b][1,3,4]oxadiazole-2,6-diamine,pyrazolo[5,1-b][1,3,4]oxadiazole-2,6-diol,2-aminopyrazolo[5,1-b][1,3,4]oxadiazole-6-ol, and6-aminopyrazolo[5,1-b][1,3,4]oxadiazole-2-ol.

(XI) Imidazo[5,1-b][1,3,4]thiadiazoles andImidazo[5,1-b][1,3,4]oxadiazoles

a. Preferred Developers

Preferred developers of formula XI are selected from the groupconsisting of imidazo[5,1-b][1,3,4]thiadiazoles andimidazo[5,1-b][1,3,4]oxadiazoles according to the following formulas:

-   -   wherein Y, D², D⁴, and D⁶ are as defined above.

Especially preferred developers of the present invention according toformulas XIa and XIb are selected from the group consisting ofimidazo[5,1-b][1,3,4]thiadiazole-7-amine,imidazo[5,1-b][1,3,4]thiadiazole-2,5,7-triamine,7-aminoimidazo[5,1-b][1,3,4]thiadiazole-2,5-diol,2,7-diaminoimidazo[5,1-b][1,3,4]thiadiazole-5-aminoimidazo[5,1-b][1,3,4]thiadiazole-2,7-diol,2,5-diaminoimidazo[5,1-b][1,3,4]thiadiazole-7-ol,imidazo[5,1-b][1,3,4]oxadiazole-7-amine,imidazo[5,1-b][1,3,4]oxadiazole-2,5,7-triamine,7-aminoimidazo[5,1-b][1,3,4]oxadiazole-2,5-diol,2,7-diaminoimidazo[5,1-b][1,3,4]oxadiazole-5-ol,5-aminoimidazo[5,1-b][1,3,4]oxadiazole-2,7-diol, and2,5-diaminoimidazo[5,1-b][1,3,4]oxadiazole-7-ol.

b. Preferred Couplers

Preferred couplers of formula XI are selected from the group consistingof imidazo[5,1-b][1,3,4]thiadiazoles andimidazo[5,1-b][1,3,4]oxadiazoles according to the following formulas:

-   -   wherein Y, D²m D⁴, and D⁶ are as defined above.

Especially preferred couplers of the present invention according toformulas XIc and XId are selected from the group consisting ofimidazo[5,1-b][1,3,4]thiadiazole-2,5-diamine, imidazo[5,1-b][1,3,4]thiadiazole-2,5-diol,2-aminoimidazo[5,1-b][1,3,4]thiadiazole-5-ol,5-aminoimidazo[5,1-b][1,3,4]thiadiazole-2-ol,imidazo[5,1-b][1,3,4]thiadiazole-2,7-diamine,imidazo[5,1-b][1,3,4]thiadiazole-2,7-diol,2-aminoimidazo[5,1-b][1,3,4]thiadiazole-7-ol,7-aminoimidazo[5,1-b][1,3,4]thiadiazole-2-ol,imidazo[5,1-b][1,3,4]oxadiazole-2,5-diamine,imidazo[5,1-b][1,3,4]oxadiazole-2,5-diol,2-aminoimidazo[5,1-b][1,3,4]oxadiazole-5-ol,5-aminoimidazo[5,1-b][1,3,4]oxadiazole-2-ol,imidazo[5,1-b][1,3,4]oxadiazole-2,7-diamine,imidazo[5,1-b][1,3,4]oxadiazole-2,7-diol,2-aminoimidazo[5,1-b][1,3,4]oxadiazole-7-ol, and7-aminoimidazo[5,1-b][1,3,4]oxadiazole-2-ol.

(XII) Imidazo[2,1-b][1,3,4]thiadiazoles andImidazo[2,1-b][1,3,4]oxadiazoles

a. Preferred Developers

Preferred developers of formula XII are selected from the groupconsisting of imidazo[2,1-b][1,3,4]thiadiazoles andimidazo[2,1-b][1,3,4]oxadiazoles according to the following formula:

-   -   wherein Y, D² and D⁶ are as defined above.

Especially preferred developers of the present invention according toformula XIIa are selected from the group consisting ofimidazo[2,1-b][1,3,4]thiadiazole-5-amine,imidazo[2,1-b][1,3,4]thiadiazole-2,5,6-triamine,5,6-diaminoimidazo[2,1-b][1,3,4]thiadiazole-2-ol,5-aminoimidazo[2,1-b][1,3,4]thiadiazole-2,6-diol,2,5-diaminoimidazo[2,1-b][1,3,4]thiadiazole-6-ol,imidazo[2,1-b][1,3,4]oxadiazole-5-amine,imidazo[2,1-b][1,3,4]oxadiazole-2,5,6-triamine,5,6-diaminoimidazo[2,1-b][1,3,4]oxadiazole-2-ol,5-aminoimidazo[2,1-b][1,3,4]oxadiazole-2,6-diol, and2,5-diaminoimidazo[2,1-b][1,3,4]oxadiazole-6-ol.

b. Preferred Couplers

Preferred couplers of formula XII are selected from the group consistingof imidazo[2,1-b][1,3,4]thiadiazoles andimidazo[2,1-b][1,3,4]oxadiazoles according to the following formula:

-   -   wherein Y, D² and D⁶ are as defined above.

Especially preferred couplers of the present invention according toformula XIIb are selected from the group consisting ofimidazo[2,1-b][1,3,4]thiadiazole-2,6-diamine,imidazo[2,1-b][1,3,4]thiadiazole-2,6-diol,2-aminoimidazo[2,1-b][1,3,4]thiadiazole-6-ol,6-aminoimidazo[2,1-b][1,3,4]thiadiazole-2-ol,imidazo[2,1-b][1,3,4]oxadiazole-2,6-diamine,imidazo[2,1-b][1,3,4]oxadiazole-2,6-diol,2-aminoimidazo[2,1-b][1,3,4]oxadiazole-6-ol, and6-aminoimidazo[2,1-b][1,3,4]oxadiazole-2-ol.

SYNTHESIS EXAMPLES

The following are non-limiting synthesis examples of the presentinvention.

Example A Pyrrolo[2,1-b][1,3]thiazole-3,6-diamine, Obtainable from theFollowing Synthesis Strategy

Reaction of glycine ethyl ester hydrochloride (CAS 623-33-6) withthiophosgene (CAS 463-71-8) gives isothiocyanate 1 (J. Amer. Chem. Soc.,1916, 38, 1556). Condensation of isothiocyanate 1 with ethylcyanoacetate (CAS 105-56-6) and sulfur leads to thiazolothionederivative 2 (Monatsch. Chem., 1981, 112, 1393). Further condensation ofcompound 2 with ethyl cyanoacetate (CAS 105-56-6) affords bicycle 3(Monatsch. Chem., 1981, 112, 1393). Hydrolysis of tris ester 3 withhydrochloric acid gives tris acid 4. Decarboxylation of acid 4 leads topyrrolo[2,1-b][1,3]thiazole-3,6-diamine 15A-4.

Example B Pyrrolo[2,1-b][1,3]thiazol-5-amine, Obtainable from theFollowing Synthesis Strategy

Reaction of pyrrole (CAS 109-97-7) with 1,2-dichloroethylene (CAS540-59-0) gives 1-ethynyl-1H-pyrrole 1 (Zh. Org. Khim., 1994, 30, 314).Reaction of 1-ethynyl-1H-pyrrole 1 with butyl lithium and sulfur givespyrrolo[2,1-b][1,3]thiazole 2 (J. Organomet. Chem., 1995, 493, 271).Nitrosation of pyrrolo[2,1-b][1,3]thiazole 2 with sodium nitrite affordsto nitroso compound 3 (see similar procedure in J. Chem. Soc., C, 1966,1908). Reduction of nitroso compound 3 with hydrogen and palladium leadsto pyrrolo[2,1-b][1,3]thiazol-5-amine 15A-5.

Example C Imidazo[2,1-b][1,3]thiazol-6-amine, Obtainable from theFollowing Synthesis Strategy

Condensation of 2-aminothiazole (CAS 96-50-4) with ethyl bromopyruvate(CAS 70-23-5) gives bicycle 1 (Farmaco Ed. Sci., 1977, 32, 735).Hydrolysis of ester 1 with potassium hydroxide leads to correspondingacid 2 (Farmaco Ed. Sci., 1977, 32, 735). Treatment of acid 2 withdiphenylphosphoryl azide (CAS 26386-88-9) in the presence oftert-butanol gives carbamate 3 (J. Med. Chem., 1991, 34, 1594).Hydrolysis of carbamate 3 with hydrochloric acid providesimidazo[2,1-b][1,3]thiazol-6-amine 15B-1 (Tetr. Lett, 1999, 40, 721).

Example D Imidazo[2,1-b][1,3]thiazole-5,6-diamine, Obtainable from theFollowing Synthesis Strategy

Reaction of 2-aminothiazole (CAS 96-50-4) with chloroacetic acid (CAS79-11-8) gives compound 1 (see Interim Report for Protocols 2 and 5 from6.11.03). Cyclization of compound 1 with phosphorus oxychloride (CAS10025-87-3) gives bicycle 2 (see Interim Report for Protocols 2 and 5from 6.11.03). Nitration of bicycle 2 with nitric acid and aceticanhydride leads to nitro derivative 3 (Pharm. Acta Helv., 1993, 68, 21).Substitution of activated chloro atom in compound 3 with4-aminomethanesulfonanilide, pyridine affords amino compound 4 (Pharm.Acta Helv., 1993, 68, 21). Reduction of compound 4 with hydrogen andpalladium gives imidazo[2,1-b][1,3]thiazole-5,6-diamine 15B-4.

Example E 5-aminoimidazo[2,1-b][1,3]thiazol-6-ol, Obtainable from theFollowing Synthesis Strategy

Reaction of 2-aminothiazole (CAS 96-50-4) with chloroacetic acid (CAS79-11-8) gives compound 1 (see Interim Report for Protocols 2 and 5 from6.11.03). Cyclization of compound 1 with phosphorus oxychloride (CAS10025-87-3) gives bicycle 2 (see Interim Report for Protocols 2 and 5from 6.11.03). Nitration of bicycle 2 with nitric acid and aceticanhydride leads to nitro derivative 3 (Pharm. Acta Helv., 1993, 68, 21).Substitution of activated chloro atom in compound 3 with sodiumhydroxide affords hydroxy compound 4. Reduction of compound 4 withhydrogen and palladium gives 5-aminoimidazo[2,1-b][1,3]thiazol-6-ol15B-5.

Example F Imidazo[5,1-b][1,3]thiazol-7-amine, Obtainable from theFollowing Synthesis Strategy

Bromination of imidazole (CAS 288-32-4) with bromine gives4,5-dibromoimidazole 1 (J. Chem. Soc., 1922, 952). Reduction of compound1 with sodium sulfite leads to 4-bromoimidazole 2 (J. Chem. Soc., 1922,952). Nitration of compound 2 with a mixture of nitric and sulfuric acidaffords compound 3 (J. Chem. Soc., 1922, 952). Reaction of compound 3with a mixture of hydrogen sulfide and ammonia in water gives compound 4(J. Amer. Chem. Soc., 1957, 79, 2188). Reaction of compound 4 withchloroacetaldehyde (CAS 107-20-0) leads to compound 5 (Khim.Geterotsikl. Soedin., 1965, 313). Cyclisation of this compound withphosphorus oxychloride affords compound 6 (Khim. Geterotsikl. Soedin.,1967, 93). Reduction of compound 6 with hydrogen under palladium affordsimidazo[5,1-b][1,3]thiazol-7-amine 3-1-1.

Example G Imidazo[5,1-b][1,3]oxazol-7-amine, Obtainable from theFollowing Synthesis Strategy

Bromination of 2-methylimidazole (CAS 693-98-1) with bromine givesimidazole 1 (J. Chem. Soc., 1922, 2628). Reduction of compound 1 withsodium sulfite leads to imidazole 2 (J. Chem. Soc., 1922, 2628).Nitration of compound 2 with a mixture of nitric and sulfuric acidaffords compound 3 (J. Chem. Soc., 1922, 2628). Reaction of compound 3with chloroacetaldehyde (CAS 107-20-0) leads to compound 4 (see similarprocedure in Khim. Geterotsikl. Soedin., 1981, 833). Cyclization ofcompound 4 with potassium tert-butoxide gives compound 5 (see similarprocedure in Heterocycles, 1999, 50, 1081). Reduction of compound 6 withhydrogen under palladium affords compoundimidazo[5,1-b][1,3]oxazol-7-amine 3-2-3.

Example H Imidazo[2,1-b][1,3,4]thiadiazol-6-amine, Obtainable from theFollowing Synthesis Strategy

Reaction of chloroacetyl chloride (CAS 79-04-9) with methyl carbamate(CAS 598-55-0) gives compound 1 (J. Chem. Soc., 1960, 983). Reaction ofcompound 1 with 2-amino-1,3,4-thiadiazole (CAS 4005-51-0) leads tocompound 2 (Farmaco Ed. Sci., 1985, 40, 34). Reaction of compound 2 withpolyphosphoric acid affords compound 3 (Farmaco Ed. Sci., 1985, 40, 34).Hydrolysis of carbamate 3 with hydrochloric acid providesimidazo[2,1-b][1,3,4]thiadiazol-6-amine 12-1-4.

Example I 2,3,6-trimethylpyrrolo[2,1-b]thiazol-5-ol, Obtainable from theFollowing Synthesis Strategy

Reaction of aminoacetonitrile hydrochloride (CAS 6011-14-9) with benzoylchloride (CAS 98-88-4) gives compound 1 (J. Org. Chem., 1996, 61, 778).Reaction of compound 1 with hydrogen sulfide and ammonia leads tothioamide 2 (Am. Chem. J., 1912, 47, 239). Condensation of thioamide 2with 3-bromo-2-butanone (CAS 814-75-5) affords thiazole 3 (Lieb. Ann.,1964, 676, 141). Cyclization of thiazole 3 with bromoacetone (can beobtained by bromination of acetone with bromine (Org. Synth., 1930, 10,12)) gives bicycle 4 (Lieb. Ann., 1964, 676, 141). Hydrolysis of bicycle4 with hydrochloric acid can produce hydroxy compound 15A-3 (see similarprocedure in Lieb. Ann., 1964, 676, 141).

Example J 6-Methyl-pyrazolo[5,1-b]thiazole-7-amine 7, Obtainable fromthe Following Synthesis Strategy

Treatment of 2-mesitylsulfonyl chloride (CAS 773-64-8) with tert-butylN-hydroxycarbamate (CAS 36016-38-3) leads to compound 1 (Synthesis,1972, 140). Hydrolysis of compound 1 with trifluoroacetic acid givescompound 2 (Synthesis, 1972, 140). Obtain compound 3 by the reaction ofchloroacetaldehyde (CAS 107-20-0) with thioacetamide (CAS 62-55-5)(Lieb. Ann., 1889, 250, 269). Amination of compound 3 with compound 2leads to salt 4 (Synthesis, 1974, 126). Condensation of compound 4 withacetic anhydride affords bicycle 5 (Chem. Pharm. Bull., 1974, 22, 482).Nitrosation of compound 5 with sodium nitrite and hydrochloric acidgives compound 6 (Chem. Pharm. Bull., 1974, 22, 482). Reduction ofcompound 6 with hydrogen under palladium affords6-methylpyrazolo[5,1-b][1,3]thiazol-7-amine 7.

Example K Imidazo[5,1-b]thiazole-7-amine 7, Obtainable from theFollowing Synthesis Strategy

Bromination of imidazole (CAS 288-32-4) with bromine gives4,5-dibromoimidazole 1 (J. Chem. Soc., 1922, 952). Reduction of compound1 with sodium sulfite leads to 4-bromoimidazole 2 (J. Chem. Soc., 1922,952). Nitration of compound 2 with a mixture of nitric and sulfuric acidaffords compound 3 (J. Chem. Soc., 1922, 952). Reaction of compound 3with a mixture of hydrogen sulfide and ammonia in water gives compound 4(J. Amer. Chem. Soc., 1957, 79, 2188). Reaction of compound 4 withchloroacetaldehyde (CAS 107-20-0) leads to compound 5 (Khim.Geterotsikl. Soedin., 1965, 313). Cyclisation of this compound withphosphorus oxychloride affords compound 6 (Khim. Geterotsikl. Soedin.,1967, 93). Reduction of compound 6 with hydrogen under palladium affordsimidazo[5,1-b][1,3]thiazol-7-amine 7.

Example L 2-Methyl-imidazo[5,1-b]oxazol-7-amine 6, Obtainable from theFollowing Synthesis Strategy

Bromination of 2-methylimidazole (CAS 693-98-1) with bromine givesimidazole 1 (J. Chem. Soc., 1922, 2628). Reduction of compound 1 withsodium sulfite leads to imidazole 2 (J. Chem. Soc., 1922, 2628).Nitration of compound 2 with a mixture of nitric and sulfuric acidaffords compound 3 (J. Chem. Soc., 1922, 2628). Reaction of compound 3with chloroacetone (CAS 78-95-5) leads to compound 4 (see similarprocedure in Khim. Geterotsikl. Soedin., 1981, 833). Cyclization ofcompound 4 with potassium tert-butoxide gives compound 5 (see similarprocedure in Heterocycles, 1999, 50, 1081). Reduction of compound 5 withhydrogen under palladium affords compound2-methylimidazo[5,1-b][1,3]oxazol-7-amine 6.Keratin Dyeing Composition Components

The inventive compositions for the oxidative dyeing of keratin fiberscomprise the hair-dyeing compound described above in the hair-dyeingcompounds section and a medium suitable for dyeing. The inventivecompositions may further comprise additional components known,conventionally used, or otherwise effective for use in oxidative dyecompositions, including but limited to: developer dye compounds; couplerdye compounds; direct dyes; oxidizing agents; thickeners; chelants; pHmodifiers and buffering agents; carbonate ion sources and radicalscavenger systems; anionic, cationic, nonionic, amphoteric orzwitterionic surfactants, or mixtures thereof; anionic, cationic,nonionic, amphoteric or zwitterionic polymers, or mixtures thereof;fragrances; buffers; dispersing agents; peroxide stabilizing agents;natural ingredients, e.g. proteins and protein derivatives, and plantmaterials (e.g. aloe, chamomile and henna extracts); silicones (volatileor non-volatile, modified or non-modified), film-forming agents,ceramides, preserving agents; and opacifiers.

Some adjuvants referred to above, but not specifically described below,which are suitable are listed in the International Cosmetics IngredientDictionary and Handbook, (8^(th) ed.; The Cosmetics, Toiletry, andFragrance Association). Particularly, vol. 2, sections 3 (ChemicalClasses) and 4 (Functions) are useful in identifying specific adjuvantsto achieve a particular purpose or multipurpose.

A. Medium Suitable for Dyeing

The medium suitable for dyeing may be selected from water, or a mixtureof water and at least one organic solvent to dissolve the compounds thatwould not typically be sufficiently soluble in water. Suitable organicsolvents for use herein include, but are not limited to: C1 to C4 loweralkanols (e.g., ethanol, propanol, isopropanol), aromatic alcohols (e.g.benzyl alcohol and phenoxyethanol); polyols and polyol ethers (e.g.,carbitols, 2-butoxyethanol, propylene glycol, propylene glycolmonomethyl ether, diethylene glycol monoethyl ether, monomethyl ether,hexylene glycol, glycerol, ethoxy glycol), and propylene carbonate. Whenpresent, organic solvents are typically present in an amount rangingfrom 1% to 30%, by weight, of the composition. Preferred solvents arewater, ethanol, propanol, isopropanol, glycerol, 1,2-propylene glycol,hexylene glycol, ethoxy diglycol, and mixtures thereof. Additionalmediums suitable for dyeing may include oxidizing agents as describedbelow.

B. Auxiliary Developers

Suitable developers for use in the compositions described hereininclude, but are not limited to p-phenylenediamine derivatives, e.g.benzene-1,4-diamine (commonly known as p-phenylenediamine),2-methyl-benzene-1,4-diamine, 2-chloro-benzene-1,4-diamine,N-phenyl-benzene-1,4-diamine, N-(2-ethoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known asN,N-bis(2-hydroxyethyl)-p-phenylenediamine)(2,5-diamino-phenyl)-methanol, 1-(2′-Hydroxyethyl)-2,5-diaminobenzene,2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine,2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,N⁴,N⁴,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine,1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine,N-(4-amino-3-hydroxy-phenyl)acetamide, 2,6-diethylbenzene-1,4-diamine,2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-1,4-diamine,1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1,4-diamine,2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,N,N-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol,2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,N-(2-methoxyethyl)-benzene-1,4-diamine,3-[(4-aminophenyl)amino]propan-1-ol,3-[(4-aminophenyl)-amino]propane-1,2-diol,N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; p-aminophenol derivativessuch as: 4-amino-phenol (commonly known as p-aminophenol),4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,4-amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene,4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol,4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol,4-amino-2-fluoro-phenol; 1-Hydroxy-2,4-diaminobenzene;1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene; 2,4-Diamino-5-methylphenetol;o-phenylenediamine derivatives such as: 3,4-Diaminobenzoic acid andsalts thereof; o-aminophenol derivatives such as: 2-amino-phenol(commonly known as o-aminophenol), 2,4-diaminophenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; andheterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonlyknown as 2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,N²,N²-dimethyl-pyridine-2,5-diamine,2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol,6-methoxy-N²-methyl-pyridine-2,3-diamine,2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine,pyrazolo[1,5-a]-pyrimidine-3,7-diamine,5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2,5,6,7-tetramethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2-methylpyrazolo[1,5-a]pyrimidin-3,7-diamine hydrochloride;4-Hydroxy-2,5,6-triaminopyrimidine;1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and1-Hydroxyethyl-4,5-diaminopyrazole sulphate.

Additional developers are selected from the group consisting ofN-(3-furylmethyl)benzene-1,4-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(2-furylmethyl)benzene-1,4-diamine;N-Thiophen-2-ylmethyl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino-propenyl]-benzene-1,4-diamine;2-(6-Methyl-pyridin-2-yl)-benzene-1,4-diamine;2-Pyridin-2-yl-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-Thiazol-2-yl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide; 3′-Fluoro-biphenyl-2,5-diamine;2-Propenyl-benzene-1,4-diamine; 2′-Chloro-biphenyl-2,5-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(3-furylmethyl)benzene-1,4-diamine; 4′-Methoxy-biphenyl-2,5-diamine;N-(4-Amino-benzyl)-benzene-1,4-diamine;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4′-triaminehydrochloride; 5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diaminehydrochloride; 5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;4-Amino-2-propylaminomethyl-phenol; hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide;hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride hydrochloride;5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride;2′,4′-Diamino-biphenyl-4-ol; hydrochloride;5-Cyclobutylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol;hydrochloride; 2′,4′-Diamino-biphenyl-4-ol hydrochloride;Biphenyl-2,4,4′-triamine;5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamidehydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride;4-Amino-2-(isopropylamino-methyl)-phenol hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol hydrochloride;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol; and5-Cyclobutylamino-2-methyl-phenol.

Preferred developers include but are not limited to: p-phenylenediaminederivatives such as: 2-methyl-benzene-1,4-diamine; benzene-1,4-diamine;1-(2,5-diamino-phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol;N-(2-methoxyethyl)benzene-1,4-diamine;2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;1-(2,5-diaminophenyl)ethane-1,2-diol;1-(2′-Hydroxyethyl)-2,5-diaminobenzene;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; and mixtures thereof;p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino-phenol,4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol;1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;1-Hydroxy-2,4-diaminobenzene; 1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene;4-Amino-2-aminomethylphenol; 2,4-Diamino-5-methylphenetol;4-Amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene;1-methoxy-2-amino-4-(2′hydroxyethylamino)benzene; 5-aminosalicylic acidand salts thereof; and mixtures thereof; o-phenylenediamine derivativessuch as: 3,4-Diaminobenzoic acid and salts thereof; o-aminophenolderivatives such as: 2-amino-phenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide;2-amino-4-methyl-phenol; and mixtures thereof; and heterocyclicderivatives such as: pyrimidine-2,4,5,6-tetramine;1-methyl-1H-pyrazole-4,5-diamine;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol;1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine;1-(benzyl)-1H-pyrazole-4,5-diamine; N²,N²-dimethyl-pyridine-2,5-diamine;4-Hydroxy-2,5,6-triaminopyrimidine;1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and mixtures thereof.

More preferred developers include: 2-methyl-benzene-1,4-diamine;benzene-1,4-diamine; N,N-Bis(2-hydroxyethyl)-p-phenylenediamine;4-amino-phenol; 4-methylamino-phenol; 4-amino-3-methyl-phenol;1-Hydroxy-2,4-diaminobenzene; 2-amino-phenol; 2-amino-5-methyl-phenol;2-amino-6-methyl-phenol; 1-methyl-1H-pyrazole-4,5-diamine;1-Hydroxyethyl-4,5-diaminopyrazole sulphate;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol; and mixtures thereof.

C. Auxiliary Couplers

Suitable couplers for use in the compositions described herein include,but are not limited to: phenols, resorcinol and naphthol derivativessuch as: naphthalene-1,7-diol, benzene-1,3-diol,4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol,2-methyl-benzene-1,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonicacid, 2-isopropyl-5-methylphenol,1,2,3,4-tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol,4-hydroxy-naphthalene-1-sulfonic acid, benzene-1,2,3-triol,naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-diol,4,6-dichlorobenzene-1,3-diol, 2,3-dihydroxy-[1,4]naphthoquinone; and1-Acetoxy-2-methylnaphthalene; m-phenylenediamines such as:2,4-diaminophenol, benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol,2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-mehyl-benzene-1,3-diamine,2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(2,4-diamino-phenyl)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-aceticacid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,4-ethoxy-6-methyl-benzene-1,3-diamine,2-(2,4-diamino-5-methyl-phenoxy)-ethanol,4,6-dimethoxy-benzene-1,3-diamine,2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,3-(2,4-diamino-phenoxy)-propan-1-ol, N-[3-(dimethylamino)phenyl]urea,4-methoxy-6-methylbenzene-1,3-diamine,4-fluoro-6-methylbenzene-1,3-diamine,2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,3-(2,4-diaminophenoxy)-propane-1,2-diol,2-[2-amino-4-(methylamino)-phenoxy]ethanol,2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-[(3-aminophenyl)amino]ethanol,2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;N-(2-aminoethyl)benzene-1,3-diamine,4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine,1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and2,4-dimethoxybenzene-1,3-diamine; m-aminophenols such as:3-amino-phenol, 2-(3-hydroxy-4-methyl-phenylamino)-acetamide,2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,5-amino-2-(2-hydroxy-ethoxy)-phenol,2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,5-amino-4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol,3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,5-[(3-hydroxy-propyl)amino]-2-methylphenol,3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol,3-[(2-hydroxyethyl)amino]-2-methylphenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)amino-benzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene; and heterocyclic derivativessuch as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,1,3-benzodioxol-5-amine,2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,6-bromo-1,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-2,6-diamine,3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol, 1H-indole-2,3-dione,indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine,6-methoxypyridine-2,3-diamine; 3,4-dihydro-2H-1,4-benzoxazin-6-amine;4-hydroxy-N-methylindole, 1H-5-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole, 2,6-dihydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine,5-methylpyrazolo[5,1-e]-1,2,3-triazole,5-methyl-6-chloropyrazolo[5,1-e]-1,2,3,-triazole,5-phenylpyrazolo[5,1-e]-1,2,3-triazole and its addition salts,1H-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole tosylate,7,8-dicyano-4-methylimidazolo-[3,2-a]imidazole,2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one,2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-one, and2-methyl-5-methoxymethyl-pyrazolo[1,5-a]pyrimidin-7-one;6-Hydroxybenzomorpholine; and 3-Amino-2-methylamino-6-methoxypyridine;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one.

Additional couplers are selected from the group consisting ofN-(3-furylmethyl)benzene-1,4-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(2-furylmethyl)benzene-1,4-diamine;N-Thiophen-2-ylmethyl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-(6-Methyl-pyridin-2-yl)-benzene-1,4-diamine;2-Pyridin-2-yl-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-Thiazol-2-yl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide; 3′-Fluoro-biphenyl-2,5-diamine;2-Propenyl-benzene-1,4-diamine; 2′-Chloro-biphenyl-2,5-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(3-furylmethyl)benzene-1,4-di amine; 4′-Methoxy-biphenyl-2,5-diamine;N-(4-Amino-benzyl)-benzene-1,4-diamine;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4′-triaminehydrochloride; 5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diaminehydrochloride; 5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;4-Amino-2-propylaminomethyl-phenol; hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide;hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride hydrochloride;5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride;2′,4′-Diamino-biphenyl-4-ol; hydrochloride;5-Cyclobutylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol;hydrochloride; 2′,4′-Diamino-biphenyl-4-ol hydrochloride;Biphenyl-2,4,4′-triamine;5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamidehydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride;4-Amino-2-(isopropylamino-methyl)-phenol hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol hydrochloride;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol; and5-Cyclobutylamino-2-methyl-phenol.

Preferred couplers include but are not limited to: phenol, resorcinol,and naphthol derivatives such as: naphthalene-1,7-diol,benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol,2-methyl-naphthalen-1-ol, naphthalene-1,5-diol, naphthalene-2,7-diol,benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and2-isopropyl-5-methylphenol; 1,2,4-Trihydroxybenzene;1-Acetoxy-2-methylnaphthalene;and mixtures thereof; m-phenylenediaminederivatives such as: benzene-1,3-diamine,2-(2,4-diamino-phenoxy)-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;2,4-Diamino-5-fluorotoluenesulfatehydrate;1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and mixtures thereof;m-aminophenol derivatives such as: 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, and3-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;1-Hydroxy-3-amino-2,4-dichlorobenzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene;5-Amino-4-chloro-2-methylphenol; and mixtures thereof; and heterocyclicderivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,3-benzodioxol-5-ol,1,3-benzodioxol-5-amine, 1H-indol-4-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 1H-indole-2,3-dione,pyridine-2,6-diamine, 2-aminopyridin-3-ol, 4-hydroxy-N-methylindole,1H-5-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 6-Hydroxybenzomorpholine;2,6-Dihydroxy-3,4-dimethylpyridine; 3,5-Diamino-2,6-dimethoxypyridine;3-Amino-2-methylamino-6-methoxypyridine;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

More preferred couplers include: benzene-1,3-diol;4-chlorobenzene-1,3-diol; 2-methyl-benzene-1,3-diol;benzene-1,3-diamine; 3-amino-phenol; 5-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one; 2-aminopyridin-3-ol;1-phenyl-3-methylpyrazol-5-one;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

Additional preferred developers and couplers include5-methoxymethyl-2-aminophenol, 5-ethyl-2-aminophenol,5-phenyl-2-aminophenol, and 5-cyanoethyl-2-aminophenol.

Further additional preferred developers and couplers include: 5-memberedheteroaromatic keratin dyeing compounds with one, two, or threeheteroatoms relating to the following compounds:

-   -   wherein Z is selected from the group consisting of S and O;    -   wherein Y is selected from the group consisting of NA¹, S and O;        Bicyclic fused 5-5 heteroaromatic keratin dyeing compounds with        two or three heteroatoms relating to the following compounds:    -   wherein Y and Z are independently selected from the group        consisting of NA¹, S and O;        Tricyclic 5-6-5 heteroaromatic keratin dyeing compounds having        two heteroatoms according to the following formulas:    -   wherein Y and Z are selected from the group consisting of NA¹,        S, and O;        Bicyclic 5-6 heteroaromatic keratin dyeing compounds with one        ring junction nitrogen and one or two extra heteroatoms        according to the following formulas:        Tricyclic fused 6-5-6 heteroaromatic keratin dyeing compounds        having one heteroatom according to the following formula:    -   wherein Y is independently selected from the group consisting of        NA¹, S and O;        5-membered aza heteroaromatic keratin dyeing compounds with an        N-hydroxy or N-amino group and derivatives thereof, according to        the following formulas:    -   wherein B₁, B₂, B₃, and B₄ are selected from the group        consisting of CH and N;    -   wherein the corresponding R¹, R², R³, and R⁴ is absent when B is        N;        Bicyclic 5-6 systems of aza heteroaromatic keratin dyeing        compounds wherein the 5-membered rings have one to three        nitrogen atoms and an N-hydroxy or N-amino group and derivatives        thereof, according to the following formulas:    -   wherein B₁ and B₂ are independently selected from CH or N;    -   wherein the corresponding R¹ and R² is absent when B is N;        Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing        compounds with an N-hydroxy or N-amino group and derivatives        thereof, according to the following formulas:        Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing        compounds having a ring junction nitrogen and an N-hydroxy or        N-amino group and derivatives thereof, according to the        following formulas:        Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing        compounds having a ring junction nitrogen and an N-hydroxy or        N-amino group and derivatives thereof, according to the        following formulas:    -   wherein B₁, B₂, B₃, B₄, and B₅ are selected from the group        consisting of CH and N;    -   wherein the corresponding R1,R2, R3, R4, and R5 is absent when B        is N;    -   wherein all of the aforementioned R groups are the same or        different and are selected from the group consisting of:    -   (a) C-linked monovalent substituents selected from the group        consisting of:        -   (i) substituted or unsubstituted, straight or branched,            alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,            aliphatic, heteroaliphatic, or heteroolefinic systems,        -   (ii) substituted or unsubstituted, mono- or poly-cyclic            aliphatic, aryl, or heterocyclic systems, and        -   (iii) substituted or unsubstituted, mono-, poly-, or            per-fluoro alkyl systems; wherein said systems of (i), (ii)            and (iii) comprise from about 1 to about 10 carbon atoms and            from about 0 to about 5 heteroatoms selected from the group            consisting of O, S, N, P, and Si;        -   wherein substituents of the substituted systems of the            C-linked monovalent substituents are selected from the group            consisting of amino, hydroxyl, alkylamino (linear or            branched C1-C5), dialkylamino (linear or branched C1-C5),            hydroxyalkylamino (linear or branched C1-C5),            dihydroxyalkylamino (linear or branched C1-C5), arylamino or            substituted arylamino (substituents are halogen, C1-C5            alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5            alkylamino), heteroarylamino or substituted heteroarylamino            (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,            trifluoromethyl, amino, C1-C5 alkylamino), arylmethylamino            or substituted arylmethylamino (substituents are halogen,            C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5            alkylamino), and heteroarylmethylamino or substituted            heteroarylmethylamino (substituents are halogen, C1-C5            alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5            alkylamino),    -   (b) S-linked monovalent substituents selected from the group        consisting of SA¹, SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A²,        and SONA¹A²;    -   (c) O-linked monovalent substituents selected from the group        consisting of OA¹, and ONA¹A²;    -   (d) N-linked monovalent substituents selected from the group        consisting of NA¹A², (NA¹A²A³)⁺, NA¹OA², NA¹SA², NO₂, N═NA¹,        N═NOA¹, and NA═CN, NA¹NA²A³;    -   (e) monovalent substituents selected from the group consisting        of COOA¹, CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A², CN, and X;    -   (f) fluoroalkyl monovalent substituents selected from the group        consisting of mono-, poly-, and per-fluoro alkyl systems        comprising from about 1 to about 12 carbon atoms and from about        0 to about 4 heteroatoms; and    -   (g) hydrogen,    -   wherein A¹, A², and A³ are monovalent and are independently        selected from the group consisting of: H; substituted or        unsubstituted, straight or branched, alkyl, mono- or        poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic,        or heteroolefinic systems; substituted or unsubstituted, mono-        or poly-cyclic aliphatic, aryl, or heterocyclic systems; and        substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl        systems, or A¹ and A² together with nitrogen atoms to which they        are bound form a ring; wherein said systems comprise from about        1 to about 10 carbon atoms and from about 0 to about 5        heteroatoms selected from the group consisting of O, S, N, P,        and Si;    -   wherein X is a halogen selected from the group consisting of F,        Cl, Br, and I.

D. Direct Dyes

The inventive compositions may also comprise compatible direct dyes, inan amount sufficient to provide additional coloring, particularly withregard to intensity. Typically, such an amount will range from 0.05% to4%, by weight, of the composition. Suitable direct dyes include but arenot limited to: Acid Yellow 1, Acid Orange 3, Disperse Red 17, BasicBrown 17, Acid Black 52, Acid Black 1, Disperse Violet 4,4-Nitro-o-Phenylenediamine, 2-Nitro-p-Phenylenediamine, Picramic Acid,HC Red No. 13, 1,4-Bis-(2′-Hydroxyethyl)-amino-2-nitrobenzene, HC YellowNo. 5, HC Red No. 7, HC Blue No. 2, HC Yellow No. 4, HC Yellow No. 2, HCOrange No. 1, HC Red No. 1,2-Chloro-5-nitro-N-Hydroxyethyl-p-phenylenediamine, HC Red No. 3,4-Amino-3-nitrophenol, 2-Hydroxyethylamino-5-nitroanisole,3-nitro-p-Hydroxyethylaminophenol, 2-amino-3-nitrophenol,6-nitro-o-toluidine, 3-methylamino-4-nitrophenoxyethanol,2-nitro-5-glycerymethylanaline, HC Yellow No. 11, HC Violet No. 1, HCOrange No. 2, HC Orange No. 3, HC Yellow No. 9, 4-NitrophenylAminoethylurea, HC Red No. 10, HC Red No. 11, 2-Hydroxyethyl picramicacid, HC Blue No. 12, HC Yellow No. 6, Hydroxyethyl-2-nitro-p-toluidine,HC Yellow No. 12, HC Blue No. 10, HC Yellow No. 7, HC Yellow No. 10, HCBlue No. 9, N-ethyl-3-nitro PABA,4-amino-2-nitrophenyl-amine-2′-carboxylic acid,2-chloro-6-ethylamino-4-nitrophenol, 6-Nitro-2,5-pyridinediamine, HCViolet No. 2, 2-amino-6-chloro-4-nitrophenol,4-hydroxypropylamino-3-nitrophenol, HC Yellow No. 13,1,2,3,4-Tetrahydro-6-nitrochinoxalin, HC Red No. 14, HC Yellow No. 15,HC Yellow No. 14, 3-Amino-6-methylamino-2-nitropyridine,2,6-diamino-3-((pyridine-3-yl)azo)pyridine, Basic Red No. 118, BasicOrange No. 69, N-(2-nitro-4-aminophenyl)-allylamine,4-[(4-Amino-3-methylphenyl)(4-Imino-3-methyl-2,5-Cyclohexadien-1-ylidene)Methyl]-2-Methyl-benzeneamine-Hydrochloride,1H-Imidazolium,2-[[4-(dimethyl-amino)phenyl]azo]-1,3-dimethylchloride,Pyridinium, 1-methyl-4-[(methylphenyl-hydrazono)methyl]-, methylsulfate, 1H-Imidazolium, 2-[(4-aminophenyl)azo]-1,3-dimethyl, chloride,Basic Red 22, Basic Red 76, Basic Brown 16, Basic Yellow 57,7-(2′,4′-Dimethyl-5′-sulfophenylazo)-5-sulfo-8-hydroxynaphthalene, AcidOrange 7, Acid Red 33,1-(3′-Nitro-5′-sulfo-6′-oxophenylazo)-oxo-naphthalene chromium complex,Acid Yellow 23, Acid Blue 9, Basic Violet 14, Basic Blue 7, Basic Blue26, Sodium salt of mixture of mono- & disulfonic acids (mainly thelatter) of quinophthlanone or 2-quinolylindandione, Basic Red 2, BasicBlue 99, Disperse Red 15, Acid Violet 43, Disperse Violet 1, Acid Blue62, Pigment Blue 15, Acid Black 132, Basic Yellow 29, Disperse Black 9,1-(N-Methylmorpholinium-propylamino)-4-hydroxy-anthraquinonemethylsulfate, HC Blue No. 8, HC Red No. 8, HC Green No. 1, HC Red No.9, 2-Hydroxy-1,4-naphthoquinone, Acid Blue 199, Acid Blue 25, Acid Red4, Henna Red, Indigo, Cochenille, HC Blue 14, Disperse Blue 23, DisperseBlue 3, Violet 2, Disperse Blue 377, Basic Red 51, Basic Orange 31,Basic Yellow 87, and mixtures thereof. Preferred direct dyes include butare not limited to: Disperse Black 9, HC Yellow 2, HC Yellow 4, HCYellow 15, 4-nitro-o-phenylenediamine, 2-amino-6-chloro-4-nitrophenol,HC Red 3, Disperse Violet 1, HC Blue 2, Disperse Blue 3, Disperse Blue377, Basic Red 51, Basic Orange 31, Basic Yellow 87, and mixturesthereof.

E. Oxidizing Agent

The inventive compositions may comprise an oxidizing agent, present inan amount sufficient to bleach melanin pigment in hair and/or causeformation of dye chromophores from oxidative dye precursors (includingdevelopers and/or couplers when present). Typically, such an amountranges from 1% to 20%, preferably from 3% to 15%, more preferably from6% to 12%, by weight, of the developer composition. Inorganic peroxygenmaterials capable of yielding hydrogen peroxide in an aqueous medium arepreferred, and include but are not limited to: hydrogen peroxide;inorganic alkali metal peroxides (e.g. sodium periodate and sodiumperoxide); organic peroxides (e.g. urea peroxide, melamine peroxide);inorganic perhydrate salt bleaching compounds (e.g. alkali metal saltsof perborates, percarbonates, perphosphates, persilicates, andpersulphates, preferably sodium salts thereof), which may beincorporated as monohydrates, tetrahydrates, etc.; alkali metalbromates; enzymes; and mixtures thereof. Preferred is hydrogen peroxide.

F. Thickeners

The inventive compositions may comprise a thickener in an amountsufficient to provide the composition with a viscosity so that it can bereadily applied to the hair without unduly dripping off the hair andcausing mess. Typically, such an amount will be at least 0.1%,preferably at least 0.5%, more preferably, at least 1%, by weight, ofthe composition.

Preferred for use herein are salt tolerant thickeners, including but notlimited to: xanthan, guar, hydroxypropyl guar, scleroglucan, methylcellulose, ethyl cellulose (available as AQUACOTE (TM)), hydroxyethylcellulose (NATROSOL (TM)), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (available as KLUCEL (TM)), hydroxyethyl ethylcellulose, cetyl hydroxyethyl cellulose (available as NATROSOL (TM) Plus330), N-vinylpyrollidone (available as POVIDONE (TM)),Acrylates/Ceteth-20 Itaconate Copolymer (available as STRUCTURE (TM)3001), hydroxypropyl starch phosphate (available as STRUCTURE (TM) ZEA),polyethoxylated urethanes or polycarbamyl polyglycol ester (e.g.PEG-150/Decyl/SMDI copolymer (available as ACULYN(TM) 44),PEG-150/StearyI/SMDI copolymer available as ACULYN(TM) 46),trihydroxystearin (available as THIXCIN(TM)), acrylates copolymer (e.g.available as ACULYN(TM) 33) or hydrophobically modified acrylatecopolymers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer (availableas ACULYN(TM) 22), non-ionic amphophilic polymers comprising at leastone fatty chain and at least one hydrophilic unit selected frompolyether urethanes comprising at least one fatty chain, and blends ofCeteth—10 phosphate, Di-cetyl phosphate and Cetearyl alcohol (availableas CRODAFOS(TM) CES).

G. Chelants

The inventive compositions may comprise chelants in an amount sufficientto reduce the amount of metals available to interact with formulationcomponents, particularly oxidizing agents, more particularly peroxides.Typically such an amount will range from at least 0.25%, preferably atleast 0.5%, by weight, of the composition. Suitable chelants for useherein include but are not limited to: diamine-N,N′-dipolyacid,monoamine monoamide-N,N′-dipolyacid, andN,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid chelants(preferably EDDS (ethylenediaminedisuccinic acid)), carboxylic acids(preferably aminocarboxylic acids), phosphonic acids (preferablyaminophosphonic acids) and polyphosphoric acids (in particular straightpolyphosphoric acids), their salts and derivatives.

H. pH Modifiers and Buffering Agents

The inventive compositions may further comprise a pH modifier and/orbuffering agent in an amount that is sufficiently effective to adjustthe pH of the composition to fall within a range from 3 to 13,preferably from 8 to 12, more preferably from 9 to 11. Suitable pHmodifiers and/or buffering agents for use herein include, but are notlimited to: ammonia, alkanolamides such as monoethanolamine,diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,tripropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3,-propandiol and guanidium salts, alkalimetal and ammonium hydroxides and carbonates, preferably sodiumhydroxide and ammonium carbonate, and acidulents such as inorganic andinorganic acids, e.g., phosphoric acid, acetic acid, ascorbic acid,citric acid or tartaric acid, hydrochloric acid, and mixtures thereof.

I. Carbonate Ion Source and Radical Scavenger System

The inventive compositions may comprise a system comprising a source ofcarbonate ions, carbamate ions and or hydrocarbonate ions, and a radicalscavenger, in a sufficient amount to reduce damage to the hair duringthe coloring process. Typically, such an amount will range from 0.1% to15%, preferably 0.1% to 10%, more preferably 1% to 7%, by weight of thecomposition, of the carbonate ion, and from 0.1% to 10%, preferably from1% to 7%, by weight of the composition, of radical scavenger.Preferably, the radical scavenger is present at an amount such that theratio of radical scavenger to carbonate ion is from 1:1 to 1:4. Theradical scavenger is preferably selected such that it is not anidentical species as the alkalizing agent.

Suitable sources for the ions include but are not limited to: sodiumcarbonate, sodium hydrogen carbonate, potassium carbonate, potassiumhydrogen carbonate, guanidine carbonate, guanidine hydrogen carbonate,lithium carbonate, calcium carbonate, magnesium carbonate, bariumcarbonate, ammonium carbonate, ammonium hydrogen carbonate and mixturesthereof. Preferred sources of carbonate ions are sodium hydrogencarbonate and potassium hydrogen carbonate. Also preferred are ammoniumcarbonate, and ammonium hydrogen carbonate.

The radical scavenger is a species that can react with a carbonateradical to convert the carbonate radical by a series of fast reactionsto a less reactive species. Preferably, when the radical scavengercomprises an N atom, it has a pKa>7 to prevent the protonation of thenitrogen. Preferred radical scavengers may be selected from the classesof alkanolamines, amino sugars, amino acids and mixtures thereof, andmay include, but are not limited to: monoethanolamine,3-amino-1-propanol, 4-amino-1-butanol,5-amino-1-pentanol,1-amino-2-propanol, 1-amino-2-butanol, 1-amino-2-pentanol,1-amino-3-pentanol, 1-amino-4-pentanol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine,N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine,histidine, serine, tryptophan and potassium, sodium and ammonium saltsof the above and mixtures thereof. Other preferred radical scavengercompounds include benzylamine, glutamic acid, imidazole,di-tert-butylhydroxytoluene, hydroquinone, catechol and mixturesthereof.

Methods of Manufacture

The compounds of this invention may be obtained using conventionalmethods. A general description of how to make the compounds is providedabove and specific examples are provided below. The compositions of thisinvention may also be obtained using conventional methods. The keratindyeing compositions may be formed as solutions, preferably as aqueous oraqueous-alcohol solutions. The hair dye product compositions maypreferably be formed as thick liquids, creams, gels, or emulsions whosecomposition is a mixture of the dye compound and other dye ingredientswith conventional cosmetic additive ingredients suitable for theparticular preparation.

Methods of Use

The inventive keratin dyeing compositions may be used by admixing themwith a suitable oxidant, which reacts with the oxidative dye precursorsto develop the hair dye product composition. The oxidant is usuallyprovided in an aqueous composition, which normally is provided as aseparate component of the finished keratin dyeing product system andpresent in a separate container. Upon mixing the keratin dyeingcomposition, the adjuvants are provided in the hair dye composition asit is applied to the hair to achieve desired product attributes, e.g.,pH, viscosity, rheology, etc.

The keratin dyeing composition, as it is applied to the hair, can beweakly acidic, neutral or alkaline according to their composition,typically having a pH from 6 to 11, preferably from 7 to 10, morepreferably from 8 to 10. The pH of the developer composition istypically acidic, and generally the pH is from 2.5 to 6.5, preferablyfrom 3 to 5. The pH of the hair compositions may be adjusted using a pHmodifier as mentioned above.

In order to use the keratin dyeing composition, the above-describedcompositions are mixed immediately prior to use and a sufficient amountof the mixture is applied to the hair, according to the hair abundance,generally from 60 to 200 grams. Upon such preparation the hair dyecomposition is applied to the hair to be dyed and remains in contactwith the hair for an amount of time effective to dye the hair.Typically, the hair dye composition is allowed to act on the hair for 2to 60, preferably 15 to 45, more preferably, 30 minutes, at atemperature ranging from 15° to 50° C. Thereafter, the hair is rinsedwith water, to remove the hair dye composition and dried. If necessary,the hair is washed with a shampoo and rinsed, e.g., with water or aweakly acidic solution, such as a citric acid or tartaric acid solution,and dried. Optionally, a separate conditioning product may also beprovided.

Together, components of the keratin dyeing composition form a system fordyeing hair. This system may be provided as a kit comprising in a singlepackage separate containers of the keratin dyeing composition componentsor other hair treatment product, and instructions for use.

EXAMPLES

The following are non-limiting examples of the compositions of thepresent invention. The examples are given solely for the purpose ofillustration and are not to be construed as limitations of the presentinvention, as many variations thereof are possible without departingfrom the spirit and scope of the invention, which would be recognized byone of ordinary skill in the art. In the examples, all concentrationsare listed as weight percent, unless otherwise specified. As usedherein, “minors” refers to those optional components such aspreservatives, viscosity modifiers, pH modifiers, fragrances, foamboosters, and the like. As is apparent to one of ordinary skill in theart, the selection of these minors will vary depending on the physicaland chemical characteristics of the particular ingredients selected tomake the present invention as described herein.

The following compositions can be used for dyeing hair. Mix the dyeingcomposition with an equal weight of a 20-volume hydrogen peroxidesolution (6% by weight). Apply the resulting mixture to the hair andpermit it to remain in contact with the hair for 30 minutes. Shampoodyed hair and rinse with water and dry. Common base (CB) for dyeingIngredients Weight (g) Propylene glycol 9.5 Ammonium hydroxide 5Ethoxydiglycol 4 Ethanolamine 4.5 Oleic acid 1 Hexylene glycol 6Cocamidopropyl betaine 3.5 Oleth-10 0.3 Oleth-2 0.3 Dilinoleic acid 1.5C12-C15 Pareth-3 0.5 Soytrimonium chloride 7 Sodium metasilicate 0.05Erythorbic acid 0.5 EDTA 0.03 Sodium sulfite 0.31-Phenyl-3-methyl-5-pyrazolone 0.2 Ingredients 1 2 3 4 5 6 7Imidazo[2,1-b][1,3]thiazole-5,6- 0.05 0.04 0.03 0.01 0.05 0.15 0.2diamine N,N-Bis(2-hydroxyetyl)-p- 0.1 0.02 phenylendiamine 4-Aminophenol0.2 0.02 0.3 0.2 0.4 4-Amino-2-methylphenol 0.4 0.2 3-Aminophenol 0.15-Amino-2-methylphenol 0.02 0.02 0.02 0.04 1-Naphthol 0.05 Resorcinol0.15 0.1 0.1 0.4 0.1 0.5 0.4 2-Methylresorcinol 0.41-Hydroxyethyl-4,5-diaminopyrazole 0.2 Common base (CB) 44.18 44.1844.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qs qs Ingredients 8 910 11 12 13 14 5-aminoimidazo[2,1-b][1,3]thiazol-6- 0.3 0.2 0.2 0.1 0.10.2 0.6 ol N,N-Bis(2-hydroxyetyl)-p- 0.33 0.02 phenylendiamine4-Aminophenol 0.5 0.7 0.9 1.2 0.3 4-Amino-2-methylphenol 1 1.23-Aminophenol 0.3 5-Amino-2-methylphenol 0.4 0.4 2.5 2.5 1 0.81-Naphthol Resorcinol 0.3 0.1 0.1 0.1 0.1 0.6 0.1 2-Methylresorcinol 0.40.6 0.6 1-Hydroxyethyl-4,5-diaminopyrazole 0.2 0.2 0.4 Common base (CB)44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qs qsIngredients 15 16 17 18 19 20 21 Imidazo[5,1-b][1,3]oxazol-7-amine 1 0.10.5 0.5 0.1 0.1 0.5 N,N-Bis(2-hydroxyetyl)-p- 0.1 phenylendiamine4-Aminophenol 0.4 0.8 0.1 4-Amino-2-methylphenol 0.6 0.8 3-Aminophenol1.5 1 0.1 5-Amino-2-methylphenol 1.4 0.5 0.1 0.1 1-Naphthol 0.1 0.1 0.1Resorcinol 0.5 0.2 0.2 0.5 2-Methylresorcinol 0.5 0.8 0.11-Hydroxyethyl-4,5-diaminopyrazole 0.6 2 1.5 Common base (CB) 44.1844.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qs qsIngredients 22 23 24 25 26 27 28 Pyrrolo[2,1-b][1,3]thiazole-3,6- 0.30.5 0.4 0.3 diamine Imidazo[2,1-b][1,3]thiazol-6-amine 0.5 0.4 0.3N,N-Bis(2-hydroxyetyl)-p- 0.1 0.1 0.3 0.1 0.3 phenylendiaminep-Phenylenediamine 0.4 0.4 4-Aminophenol 0.5 0.1 0.2 0.1 0.24-Amino-2-methylphenol 1 1 3-Aminophenol 0.3 0.2 0.25-Amino-2-methylphenol 0.4 0.2 0.5 0.4 0.2 0.5 1-Naphthol 0.1 0.1Resorcinol 0.3 0.2 0.4 0.3 0.2 0.4 0.3 2-Methylresorcinol 0.4 0.2 0.21-Hydroxyethyl-4,5-diaminopyrazole 0.5 0.1 0.3 0.5 0.1 0.3 Common base(CB) 44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qsqs Ingredients 29 30 31 32 33 34 35 Imidazo[2,1-b][1,3,4] thiadiazol-6-0.3 0.5 0.4 0.3 amine 2,3,6-trimethylpyrrolo [2,1-b]thiazol- 0.5 0.4 0.35-ol N,N-Bis(2-hydroxyetyl)-p- 0.1 0.1 0.3 0.1 0.3 phenylendiaminep-Phenylenediamine 0.4 0.4 4-Aminophenol 0.5 0.1 0.2 0.1 0.24-Amino-2-methylphenol 1 1 3-Aminophenol 0.3 0.2 0.25-Amino-2-methylphenol 0.4 0.2 0.5 0.4 0.2 0.5 1-Naphthol 0.1 0.1Resorcinol 0.3 0.2 0.4 0.3 0.2 0.4 0.3 2-Methylresorcinol 0.4 0.2 0.21-Hydroxyethyl-4,5-diaminopyrazole 0.5 0.1 0.3 0.5 0.1 0.3 Common base(CB) 44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qsqs Ingredients 36 37 38 39 40 41 42 Pyrrolo[2,1-b]thiazole-7-amine 0.050.04 0.03 0.01 0.05 0.15 0.2 N,N-Bis(2-hydroxyetyl)-p- 0.1 0.02phenylendiamine 4-Aminophenol 0.2 0.02 0.3 0.2 0.44-Amino-2-methylphenol 0.4 0.2 3-Aminophenol 0.1 5-Amino-2-methylphenol0.02 0.02 0.02 0.04 1-Naphthol 0.05 Resorcinol 0.15 0.1 0.1 0.4 0.1 0.50.4 2-Methylresorcinol 0.4 1-Hydroxyethyl-4,5-diaminopyrazole 0.2 Commonbase (CB) 44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qsqs qs Ingredients 43 44 45 46 47 48 49 Pyrazolo[5,1-b]thiazole-7-amine0.3 0.2 0.2 0.1 0.1 0.2 0.6 N,N-Bis(2-hydroxyetyl)-p- 0.33 0.02phenylendiamine 4-Aminophenol 0.5 0.7 0.9 1.2 0.3 4-Amino-2-methylphenol1 1.2 3-Aminophenol 0.3 5-Amino-2-methylphenol 0.4 0.4 2.5 2.5 1 0.81-Naphthol Resorcinol 0.3 0.1 0.1 0.1 0.1 0.6 0.1 2-Methylresorcinol 0.40.6 0.6 1-Hydroxyethyl-4,5-diaminopyrazole 0.2 0.2 0.4 Common base (CB)44.18 44.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qs qsIngredients 50 51 52 53 54 55 56 Imidazo[5,1-b]thiazole-7-amine 1 0.10.5 0.5 0.1 0.1 0.5 N,N-Bis(2-hydroxyetyl)-p- 0.1 phenylendiamine4-Aminophenol 0.4 0.8 0.1 4-Amino-2-methylphenol 0.6 0.8 3-Aminophenol1.5 1 0.1 5-Amino-2-methylphenol 1.4 0.5 0.1 0.1 1-Naphthol 0.1 0.1 0.1Resorcinol 0.5 0.2 0.2 0.5 2-Methylresorcinol 0.5 0.8 0.11-Hydroxyethyl-4,5-diaminopyrazole 0.6 2 1.5 Common base (CB) 44.1844.18 44.18 44.18 44.18 44.18 44.18 Water qs qs qs qs qs qs qs

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

All documents cited in the Background, Summary of the Invention, andDetailed Description of the Invention are, in relevant part,incorporated herein by reference; the citation of any document is not tobe construed as an admission that it is prior art with respect to thepresent invention.

1. A keratin dyeing composition comprising: (A) a medium suitable fordyeing; and (B) one or more bicyclic 5-5 heteroaromatic compounds havinga ring junction nitrogen according to the following formulas:

wherein Y is selected from the group consisting of S and O; wherein R¹,R², R⁴, R⁵, and R⁶ are the same or different and are selected from thegroup consisting of: (a) C-linked monovalent substituents selected fromthe group consisting of: (i) substituted or unsubstituted, straight orbranched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,aliphatic, heteroaliphatic, or heteroolefinic systems, (ii) substitutedor unsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclicsystems, and (iii) substituted or unsubstituted, mono-, poly-, orper-fluoro alkyl systems; wherein said systems of (i), (ii) and (iii)comprise from about 1 to about 10 carbon atoms and from about 0 to about5 heteroatoms selected from the group consisting of O, S, N, P, and Si;(b) S-linked monovalent substituents selected from the group consistingof SA¹, SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²; (c)O-linked monovalent substituents selected from the group consisting ofOA¹, and ONA¹A²; (d) N-linked monovalent substituents selected from thegroup consisting of NA¹A², (NA¹A²A³)⁺, NA¹OA², NA¹SA², NO₂, N═NA¹,N═NOA¹, NA¹CN, and NA¹NA²A³; (e) monovalent substituents selected fromthe group consisting of COOA¹, CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A², CN, andX; (f) fluoroalkyl monovalent substituents selected from the groupconsisting of mono-, poly-, and per-fluoro alkyl systems comprising fromabout 1 to about 12 carbon atoms and from about 0 to about 4heteroatoms; and (g) hydrogen wherein A¹, A², and A³ are monovalent andare each independently selected from the group consisting of H;substituted or unsubstituted, straight or branched, alkyl, mono- orpoly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, orheteroolefinic systems; substituted or unsubstituted, mono- orpoly-cyclic aliphatic, aryl, or heterocyclic systems; and substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems, or A¹ and A²together with nitrogen atom to which they are bound form a ring; whereinsaid systems comprise from about 1 to about 10 carbon atoms and fromabout 0 to about 5 heteroatoms selected from the group consisting of O,S, N, P, and Si; and wherein X is a halogen selected from the groupconsisting of F, Cl, Br, and I.
 2. The composition of claim 1 whereinsaid R¹, R², R⁴, R⁵, and R⁶ are each independently selected from thegroup consisting of a hydrogen atom; a halogen atom; an aminosubstituent; a hydroxyl substituent; a cyano substituent; a C1-C₄ alkylsubstituent; a trifluoromethyl substituent; an alkylamino substituent; ahydroxyalkylamino substituent; an acetylamido substituent; a carboxylsubstituent or its esters; an alkoxy substituent; an alkoxyalkylsubstituent; a carbamoyl substituent; an alkylcarbamoyl substituent; ahydroxyalkylcarbamoyl substituent; an amido substituent; an alkylamidosubstituent; an alkylcarbonyl substituent; an alkoxycarbonylsubstituent; an aryloxy substituent; an acyloxy substituent; analkylthio substituent; an arylthio substituent; a heteroarylthiosubstituent; a heteroaryloxy substituent; a thiocyano substituent; a 3-,4-, 5-, 6-, or 7-membered heterocycle having at least one nitrogen,oxygen or sulfur atom; an aryl substituent which is optionallysubstituted; a sulfonyl substituent; a sulfinyl substituent; aphosphonyl substituent; a sulfamoyl substituent; a siloxy substituent;an acyloxy substituent; a carbamoyloxy substituent; a sulphonamidesubstituent; an imide substituent; a ureido substituent; asulfamoylamino substituent; an alkoxycarbonylamino substituent; anaryloxycarbonylamino substituent; an aryloxycarbonyl substituent; and abenzenesulfonamido substituent.
 3. The composition of claim 1 wherein atleast one of said R¹, R⁴ or R⁶ is an amino group, with at least one ofthe remaining R¹, R², R⁴, R⁵, and R⁶ being selected from substituentsbeing selected from the group consisting of Amino, hydroxyl, a 3-, 4-,5-, 6-, or 7-membered heterocycle having at least one nitrogen, oxygenor sulfur atom, Alkylamino (linear, branched, or cyclic C1-C5),Dialkylamino (linear, branched, or cyclic C1-C5), Hydroxyalkylamino(linear, branched, or cyclic C1-C5), Dihydroxyalkylamino (linear,branched, or cyclic C1-C5), Arylamino or substituted arylamino;Heteroarylamino or substituted heteroarylamino; Arylmethylamino orsubstituted arylmethylamino; and Heteroarylmethylamino or substitutedheteroarylmethylamino, wherein substituents are selected from the groupconsisting of halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, and C1-C5 alkylamino.
 4. The composition of claim 1 wherein atleast one of said R¹, R², R⁴, R⁵, and R⁶ is selected from substituentsselected from the group consisting of Amino, Hydroxyl, Alkylamino(linear, branched, or cyclic C1-C5), Hydroxyalkylamino (linear,branched, or cyclic C1-C5), Arylamino or substituted arylamino;Heteroarylamino or substituted heteroarylamino; Arylmethylamino orsubstituted arylmethylamino; and Heteroarylmethylamino or substitutedheteroarylmethylamino, wherein substituents are selected from the groupconsisting of halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,amino, and C1-C5 alkylamino.
 5. The composition of claim 1 wherein saidbicyclic 5-5 heteroaromatic compound having a ring junction nitrogen isselected from the group consisting of compounds according to thefollowing formulas:

wherein Y is selected from the group consisting of S and O; wherein D²and D⁵ are each independently selected from the group consisting ofamino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl; and whereinE¹, E², E⁴, E⁵ and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino), carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 6. The composition of claim 5wherein said bicyclic 5-5 heteroaromatic compound having a ring junctionnitrogen is selected from the group consisting ofpyrrolo[2,1-b]thiazole-5,6-diamine, 5-aminopyrrolo[2,1-b]thiazol-6-ol,pyrrolo[2,1-b]thiazol-7-amine, pyrrolo[2,1-b]thiazole-2,3-diamine,pyrrolo[2,1-b]thiazol-5-amine, 3-aminopyrrolo[2,1-b]thiazol-2-ol,pyrrolo[2,1-b]oxazole-5,6-diamine, 5-aminopyrrolo[2,1-b]oxazol-6-ol,pyrrolo[2,1-b]oxazol-7-amine, pyrrolo[2,1-b]oxazole-2,3-diamine,pyrrolo[2,1-b]oxazol-5-amine, 3-aminopyrrolo[2,1-b]oxazol-2-ol,pyrrolo[2,1-b]thiazol-6-amine, pyrrolo[2,1-b]thiazol-6-ol,6-methylpyrrolo[2,1-b]thiazole, pyrrolo[2,1-b]thiazole-3,6-diamine,pyrrolo[2,1-b]thiazole-6,7-diamine, pyrrolo[2,1-b]thiazol-2-amine,pyrrolo[2,1-b]thiazol-2-ol, pyrrolo[2,1-b]oxazol-6-amine,pyrrolo[2,1-b]oxazol-6-ol, 6-methylpyrrolo[2,1-b]oxazole,pyrrolo[2,1-b]oxazole-3,6-diamine, pyrrolo[2,1-b]oxazole-6,7-diamine,pyrrolo[2,1-b]oxazol-2-amine, and pyrrolo[2,1-b]oxazol-2-ol.
 7. Thecomposition of claim 1 wherein said bicyclic 5-5 heteroaromatic compoundhaving a ring junction nitrogen is selected from the group consisting ofcompounds according to the following formulas:

wherein Y is selected from the group consisting of S and O; wherein D²is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-phenyl, N-benzyl, methoxy, ethoxy,propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio,ethylthio, propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyland thiadiazolyl; and wherein E¹, E², E⁴, and E⁵ are each independentlyselected from the group consisting of hydrogen, chlorine, bromine,fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino), carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 8. The composition of claim 7wherein said bicyclic 5-5 heteroaromatic compound having a ring junctionnitrogen is selected from the group consisting ofpyrazolo[5,1-b]thiazol-7-amine,6-methyl-pyrazolo[5,1-b]thiazole-7-amine,pyrazolo[5,1-b]thiazole-6,7-diamine, 7-aminopyrazolo[5,1-b]thiazol-6-ol,pyrazolo[5,1-b]thiazole-2,3-diamine, 3-aminopyrazolo[5,1-b]thiazol-2-ol,pyrazolo[5,1-b]oxazol-7-amine, pyrazolo[5,1-b]oxazole-6,7-diamine,7-aminopyrazolo[5,1-b]oxazol-6-ol, pyrazolo[S,1-b]oxazole-2,3-diamine,3-aminopyrazolo[5,1-b]oxazol-2-ol, pyrazolo[5,1-b]thiazol-6-amine,pyrazolo[5,1-b]thiazol-6-ol, pyrazolo[5,1-b]thiazole-3,6-diamine,pyrazolo[5,1-b]thiazole-6,7-diamine, pyrazolo[5,1-b]thiazol-2-amine,pyrazolo[5,1-b]thiazol-2-ol, pyrazolo[5,1-b]oxazol-6-amine,pyrazolo[5,1-b]oxazol-6-ol, pyrazolo[5,1-b]oxazole-3,6-diamine,pyrazolo[5,1-b]oxazole-6,7-diamine, pyrazolo[5,1-b]oxazol-2-amine, andpyrazolo[5,1-b]oxazol-2-ol.
 9. The composition of claim 1 wherein saidbicyclic 5-5 heteroaromatic compound having a ring junction nitrogen isselected from the group consisting of compounds according to thefollowing formulas:

wherein Y is selected from the group consisting of S and O; wherein D²is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-phenyl, N-benzyl, methoxy, ethoxy,propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio,ethylthio, propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyland thiadiazolyl; and wherein E¹, E², E⁴, and E⁶ are each independentlyselected from the group consisting of hydrogen, chlorine, bromine,fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino), carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 10. The composition of claim 9wherein said bicyclic 5-5 heteroaromatic compound having a ring junctionnitrogen is selected from the group consisting ofimidazo[5,1-b]thiazole-7-amine, imidazo[5,1-b]thiazole-5,7-diamine,imidazo[5,1-b]thiazole-3,5,7-triamine,5-aminoimidazo[5,1-b]thiazole-7-ol, imidazo[5,1-b]thiazole-7-amine,imidazo[5,1-b]thiazole-2,3-diamine, imidazo[5,1-b]thiazole-5-amine,3-aminoimidazo[5,1-b]thiazole-2-ol, imidazo[5,1-b]oxazole-5,7-diamine,5-aminoimidazo[5,1-b]oxazole-7-ol, imidazo[5,1-b]oxazole-7-amine,2-methyl-imidazo[5,1-b]oxazole-7-amine,imidazo[5,1-b]oxazole-2,3-diamine, imidazo[5,1-b]oxazole-5-amine,3-aminoimidazo[5,1-b]oxazole-2-ol, imidazo[5,1-b]thiazole-3,7-diamine,imidazo[5,1-b]thiazole-3,7-diol, imidazo[5,1-b]thiazole-3,5-diamine,imidazo[5,1-b]thiazole-2,7-diamine, imidazo[5,1-b]thiazole-2-amine,imidazo[5,1-b]thiazole-2-ol, imidazo[5,1-b]oxazole-3,7-diamine,imidazo[5,1-b]oxazole-3,7-diol, imidazo[5,1-b]oxazole-3,5-diamine,imidazo[5,1-b]oxazole-2,7-diamine, imidazo[5,1-b]oxazole-2-amine, andimidazo[5,1-b]oxazole-2-ol.
 11. The composition of claim 1 wherein saidbicyclic 5-5 heteroaromatic compound having a ring junction nitrogen isselected from the group consisting of compounds according to thefollowing formulas:

wherein Y is selected from the group consisting of S and O; wherein D²and D⁵ are each independently selected from the group consisting ofamino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl; and whereinE¹, E², E⁵, and E⁶ are each independently selected from the groupconsisting of hydrogen, chlorine, bromine, fluorine, amino, hydroxyl,cyano, methyl, ethyl, isopropyl, trifluoromethyl, N,N-dimethylamino,N,N-diethylamino, N-methylamino, N-ethylamino, N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino), carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 12. The composition of claim 11wherein said bicyclic 5-5 heteroaromatic compound having a ring junctionnitrogen is selected from the group consisting ofimidazo[2,1-b]thiazole-5-amine, imidazo[2,1-b]thiazole-5,6-diamine,5-amino imidazo[2,1-b]thiazole-6-ol, imidazo[2,1-b]thiazole-2,3-diamine,3-amino imidazo[2,1-b]thiazole-2-ol, imidazo[2,1-b]oxazole-5-amine,imidazo[2,1-b]oxazole-5,6-diamine, 5-amino imidazo[2,1-b]oxazole-6-ol,imidazo[2,1-b]oxazole-2,3-diamine, 3-amino imidazo[2,1-b]oxazole-2-ol,imidazo[2,1-b]thiazole-6-amine, imidazo[2,1-b]thiazole-6-ol,imidazo[2,1-b]thiazole-3,6-diamine, imidazo[2,1-b]thiazole-5,6-diamine,imidazo[2,1-b]thiazole-2-amine, imidazo[2,1-b]thiazole-2-ol,imidazo[2,1-b]oxazole-6-amine, imidazo[2,1-b]oxazole-6-ol,imidazo[2,1-b]oxazole-3,6-diamine, imidazo[2,1-b]oxazole-5,6-diamine,imidazo[2,1-b]oxazole-2-amine, and imidazo[2,1-b]oxazole-2-ol.
 13. Thecomposition of claim 1 wherein said bicyclic 5-5 heteroaromatic compoundhaving a ring junction nitrogen is selected from the group consisting ofcompounds according to the following formulas:

wherein Y is selected from the group consisting of S and O; wherein D⁵is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-phenyl, N-benzyl, methoxy, ethoxy,propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio,ethylthio, propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyland thiadiazolyl; and wherein E², E⁴, E⁵, and E⁶ are each independentlyselected from the group consisting of hydrogen, chlorine, bromine,fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino), carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 14. The composition of claim 13wherein said bicyclic 5-5 heteroaromatic compound having a ring junctionnitrogen is selected from the group consisting ofpyrrolo[2,1-b][1,3,4]thiadiazole-7-amine,pyrrolo[2,1-b][1,3,4]thiadiazole-5-amine,pyrrolo[2,1-b][1,3,4]thiadiazole-5,6-diamine,5-aminopyrrolo[2,1-b][1,3,4]thiadiazole-6-ol,pyrrolo[2,1-b][1,3,4]thiadiazole-6,7-diamine,5-aminopyrrolo[2,1-b][1,3,4]thiadiazole-2-ol,pyrrolo[2,1-b][1,3,4]oxadiazole-7-amine,pyrrolo[2,1-b][1,3,4]oxadiazole-5-amine,pyrrolo[2,1-b][1,3,4]oxadiazole-5,6-diamine,5-aminopyrrolo[2,1-b][1,3,4]oxadiazole-6-ol,pyrrolo[2,1-b][1,3,4]oxadiazole-6,7-diamine,5-aminopyrrolo[2,1-b][1,3,4]oxadiazole-2-ol,pyrazolo[5,1-b]thiazol-6-amine, pyrazolo[5,1-b]thiazol-6-ol,pyrazolo[5,1-b]thiazole-2,6-diamine, pyrazolo[5,1-b]thiazole-2,6-diol,pyrazolo[5,1-b]thiazol-2,7-diol, pyrazolo[5,1-b]oxazol-6-amine,pyrazolo[5,1-b]oxazol-6-ol, pyrazolo[5,1-b]oxazole-2,6-diamine,pyrazolo[5,1-b]oxazole-2,6-diol, and pyrazolo[5,1-b]oxazol-2,7-diol. 15.The composition of claim 1 wherein said bicyclic 5-5 heteroaromaticcompound having a ring junction nitrogen are selected from the groupconsisting of compounds according to the following formulas:

wherein Y is selected from the group consisting of S and O; wherein D⁵is selected from the group consisting of amino, hydroxyl,N,N-dimethylamino, N,N-diethylamino, N-methylamino, N-ethylamino,N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino,N,N-bis(hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino,N,N-bis(hydroxypropyl)amino, N-phenyl, N-benzyl, methoxy, ethoxy,propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, phenoxy, methylthio,ethylthio, propylthio, furyl, pyrazolyl, triazolyl, oxazolyl, imidazolyland thiadiazolyl; and wherein E¹, E⁴, E⁵, and E⁶ are each independentlyselected from the group consisting of hydrogen, chlorine, bromine,fluorine, amino, hydroxyl, cyano, methyl, ethyl, isopropyl,trifluoromethyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino), carboxyl,methoxy, ethoxy, propyloxy, benzyloxy, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, amido,acetamido, propionamido, butyramido, acetyl, butyryl, propionyl,phenoxy, methylthio, ethylthio, propylthio, butylthio, pyridyl,quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl,tetrazolyl, triazolyl, oxazolyl, imidazolyl, thiadiazolyl, phenyl,sulfonyl, sulphonamido, and ureido.
 16. The composition of claim 15wherein said bicyclic 5-5 heteroaromatic compound having a ring junctionnitrogen is selected from the group consisting ofpyrrolo[1,2-d][1,2,4]thiadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]thiadiazole-3,5,6-triamine,5-aminopyrrolo[1,2-d][1,2,4]thiadiazole-6-ol,pyrrolo[1,2-d][1,2,4]thiadiazole-6,7-diamine,5-pyrrolo[1,2-d][1,2,4]thiadiazole-5-amine,pyrrolo[1,2-d][1,2,4]thiadiazole-6,7-diamine,5-aminopyrrolo[1,2-d][1,2,4]thiadiazole-7-ol,pyrrolo[1,2-d][1,2,4]thiadiazole-3,6,7-triol,pyrrolo[1,2-d][1,2,4]oxadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]oxadiazole-3,5,6-triamine,5-aminopyrrolo[1,2-d][1,2,4]oxadiazole-6-ol,pyrrolo[1,2-d][1,2,4]oxadiazole-7-amine,pyrrolo[1,2-d][1,2,4]oxadiazole-5-amine,pyrrolo[1,2-d][1,2,4]oxadiazole-6,7-diamine,5-aminopyrrolo[1,2-d][1,2,4]oxadiazole-7-ol,pyrrolo[1,2-d][1,2,4]oxadiazole-3,6,7-triol,pyrrolo[1,2-d][1,2,4]thiadiazole-6,7-diamine,pyrrolo[1,2-d][1,2,4]thiadiazole-6,7-diol,pyrrolo[1,2-d][1,2,4]thiadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]thiadiazole-6-amine,pyrrolo[1,2-d][1,2,4]thiadiazole-6-ol,pyrrolo[1,2-d][1,2,4]oxadiazole-6,7-diamine,pyrrolo[1,2-d][1,2,4]oxadiazole-6,7-diol,pyrrolo[1,2-d][1,2,4]oxadiazole-5,6-diamine,pyrrolo[1,2-d][1,2,4]oxadiazole-6-amine, andpyrrolo[1,2-d][1,2,4]oxadiazole-6-ol, 2-ol.
 17. The composition of claim1 wherein said bicyclic 5-5 heteroaromatic compound having a ringjunction nitrogen is selected from the group consisting of compoundsaccording to the following formulas:

wherein Y is selected from the group consisting of S and O; and whereinD¹, D², and D⁴ are each independently selected from the group consistingof amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.
 18. Thecomposition of claim 17 wherein bicyclic 5-5 heteroaromatic compoundhaving a ring junction nitrogen is selected from the group consisting ofthiazolo[3,2-e][1,2,3]triazole-7-amine,thiazolo[3,2-e][1,2,3]triazole-2,3,7-triamine,7-aminothiazolo[3,2-e][1,2,3]triazole-2,3-diol,3,7-diaminothiazolo[3,2-e][1,2,3]traizole-2-ol,2,3-diaminothiazolo[3,2-e][1,2,3]triazole-7-ol,3,7-triaminothiazolo[3,2-e][1,2,3]triazole-2-ol,oxazolo[3,2-e][1,2,3]triazole-7-amine,oxazolo[3,2-e][1,2,3]triazole-2,3,7-triamine,7-aminooxazolo[3,2-e][1,2,3]triazole-2,3-diol,3,7-diaminooxazolo[3,2-e][1,2,3]triazole-2-ol,2,3-diaminooxazolo[3,2-e][1,2,3]triazole-7-ol,3,7-triaminooxazolo[3,2-e][1,2,3]triazole-2-ol,thiazolo[3,2-e][1,2,3]triazole-2,3-diamine,thiazolo[3,2-e][1,2,3]triazole-2,3-diol,thiazolo[3,2-e][1,2,3]triazole-2,7-diamine,2-aminothiazolo[3,2-e][1,2,3]triazole-7-ol,7-aminothiazolo[3,2-e][1,2,3]triazole-2-ol,oxazolo[3,2-e][1,2,3]triazole-2,3-diamine,oxazolo[3,2-e][1,2,3]triazole-2,3-diol,oxazolo[3,2-e][1,2,3]triazole-2,7-diamine,2-aminooxazolo[3,2-e][1,2,3]triazole-7-ol, and7-aminooxazolo[3,2-e][1,2,3]triazole-2-ol.
 19. The composition of claim1 wherein said bicyclic 5-5 heteroaromatic compound having a ringjunction nitrogen is selected from the group consisting of compoundsaccording to the following formulas:

wherein Y is selected from the group consisting of S and O; and whereinD² and D⁵ are each independently selected from the group consisting ofamino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamnino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.
 20. Thecomposition of claim 19 wherein said bicyclic 5-5 heteroaromaticcompound having a ring junction nitrogen is selected from the groupconsisting of thiazolo[3,2-b][1,2,4]triazole-2,3,6-triamine,3-aminothiazolo[3,2-b][1,2,4]triazole-2,6-diol,diaminothiazolo[3,2-b][1,2,4]triazole-6-ol,oxazolo[3,2-b][1,2,4]triazole-2,3,6-triamine,3-aminooxazolo[3,2-b][1,2,4]triazole-2,6-diol,2,3-diaminooxazolo[3,2-b][1,2,4]-triazole-6-ol, ofthiazolo[3,2-b][1,2,4]triazole-2,6-diamine,thiazolo[3,2-b][1,2,4]triazole-2,6-diol,2-aminothiazolo[3,2-b][1,2,4]triazole-6-ol,6-aminothiazolo[3,2-b][1,2,4]triazole-2-ol,oxazolo[3,2-b][1,2,4]triazole-2,6-diamine,oxazolo[3,2-b][1,2,4]triazole-2,6-diol,2-aminooxazolo[3,2-b][1,2,4]triazole-6-ol, and6-aminooxazolo[3,2-b][1,2,4]triazole-2-ol.
 21. The composition of claim1 wherein said bicyclic 5-5 heteroaromatic compound having a ringjunction nitrogen is selected from the group consisting of compoundsaccording to the following formulas:

wherein Y is selected from the group consisting of S and O; and whereinD¹, D², and D⁶ are each independently selected from the group consistingof amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.
 22. Thecomposition of claim 21 wherein said bicyclic 5-5 heteroaromaticcompound having a ring junction nitrogen is selected from the groupconsisting of thiazolo[2,3-c][1,2,4]triazole-5-amine,thiazolo[2,3-c][1,2,4]triazole-2,3,5-triamine,3-aminothiazolo[2,3-c][1,2,4]triazole-2,5-diol,2,5-diaminothiazolo[2,3-c][1,2,4]triazole-3-ol,5-aminothiazolo[2,3-c][1,2,4]triazole-2,3-diol,3,5-diaminothiazolo[2,3-c][1,2,4]triazole-2-ol,oxazolo[2,3-c][1,2,4]triazole-5-amine,oxazolo[2,3-c][1,2,4]triazole-2,3,5-triamine,3-aminooxazolo[2,3-c][1,2,4]triazole-2,5-diol,2,5-diaminooxazolo[2,3-c][1,2,4]triazole-3-ol,5-aminooxazolo[2,3-c][1,2,4]triazole-2,3-diol,3,5-diaminooxazolo[2,3-c][1,2,4]triazole-2-ol,thiazolo[2,3-c][1,2,4]triazole-2,3-diamine,thiazolo[2,3-c][1,2,4]triazole-2,3-diol,thiazolo[2,3-c][1,2,4]triazole-2,5-diol,thiazolo[2,3-c][1,2,4]triazole-2,5-diamine,oxazolo[2,3-c][1,2,4]triazole-2,3-diamine,oxazolo[2,3-c][1,2,4]triazole-2,3-diol,oxazolo[2,3-c][1,2,4]triazole-2,5-diol, andoxazolo[2,3-c][1,2,4]triazole-2,5-diamine.
 23. The composition of claim1 wherein said bicyclic 5-5 heteroaromatic compound having a ringjunction nitrogen is selected from the group consisting of compoundsaccording to the following formulas:

wherein Y is selected from the group consisting of S and O; and whereinD² and D⁵ are each independently selected from the group consisting ofamino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.
 24. Thecomposition of claim 23 wherein said bicyclic 5-5 heteroaromaticcompound having a ring junction nitrogen is selected from the groupconsisting of pyrazolo[5,1-b][1,3,4]thiadiazole-7-amine,pyrazolo[5,1-b][1,3,4]thiadiazole-2,6,7-triamine,7-aminopyrazolo[5,1-b][1,3,4]thiadiazole-2,6-diol,6,7-diaminopyrazolo[5,1-b][1,3,4]thiadiazole-2-ol,2,7-diaminopyrazolo[5,1-b][1,3,4]thiadiazole-6-ol,pyrazolo[5,1-b][1,3,4]oxadiazole-7-amine,pyrazolo[5,1-b][1,3,4]oxadiazole-2,6,7-triamine,7-aminopyrazolo[5,1-b][1,3,4]oxadiazole-2,6-diol,6,7-diaminopyrazolo[5,1-b][1,3,4]oxadiazole-2-ol,2,7-diaminopyrazolo[5,1-b][1,3,4]oxadiazole-6-ol,pyrazolo[5,1-b][1,3,4]thiadiazole-2,6-diamine,pyrazolo[5,1-b][1,3,4]thiadiazole-2,6-diol,2-aminopyrazolo[5,1-b][1,3,4]thiadiazole-6-ol,6-aminopyrazolo[5,1-b][1,3,4]thiadiazole-2-ol,pyrazolo[5,1-b][1,3,4]oxadiazole-2,6-diamine,pyrazolo[5,1-b][1,3,4]oxadiazole-2,6-diol,2-aminopyrazolo[5,1-b][1,3,4]oxadiazole-6-ol, and6-aminopyrazolo[5,1-b][1,3,4]oxadiazole-2-ol.
 25. The composition ofclaim 1 wherein said bicyclic 5-5 heteroaromatic compound having a ringjunction nitrogen is selected from the group consisting of compoundsaccording to the following formulas:

wherein Y is selected from the group consisting of S and O; and whereinD², D⁴, and D⁶ are each independently selected from the group consistingof amino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.
 26. Thecomposition of claim 25 wherein said bicyclic 5-5 heteroaromaticcompound having a ring junction nitrogen is selected from the groupconsisting of imidazo[5,1-b][1,3,4]thiadiazole-7-amine,imidazo[5,1-b][1,3,4]thiadiazole-2,5,7-triamine,7-aminoimidazo[5,1-b][1,3,4]thiadiazole-2,5-diol,2,7-diaminoimidazo[5,1-b][1,3,4]thiadiazole-5-ol,5-aminoimidazo[5,1-b][1,3,4]thiadiazole-2,7-diol,2,5-diaminoimidazo[5,1-b][1,3,4]thiadiazole-7-ol,imidazo[5,1-b][1,3,4]oxadiazole-7-amine,imidazo[5,1-b][1,3,4]oxadiazole-2,5,7-triamine,7-aminoimidazo[5,1-b][1,3,4]oxadiazole-2,5-diol,2,7-diaminoimidazo[5,1-b][1,3,4]oxadiazole-5-ol,5-aminoimidazo[5,1-b][1,3,4]oxadiazole-2,7-diol,2,5-diaminoimidazo[5,1-b][1,3,4]oxadiazole-7-ol,imidazo[5,1-b][1,3,4]thiadiazole-2,5-diamine,imidazo[5,1-b][1,3,4]thiadiazole-2,5-diol,2-aminoimidazo[5,1-b][1,3,4]thiadiazole-5-ol,5-aminoimidazo[5,1-b][1,3,4]thiadiazole-2-ol,imidazo[5,1-b][1,3,4]thiadiazole-2,7-diamine,imidazo[5,1-b][1,3,4]thiadiazole-2,7-diol,2-aminoimidazo[5,1-b][1,3,4]thiadiazole-7-ol,7-aminoimidazo[5,1-b][1,3,4]thiadiazole-2-ol,imidazo[5,1-b][1,3,4]oxadiazole-2,5-diamine,imidazo[5,1-b][1,3,4]oxadiazole-2,5-diol,2-aminoimidazo[5,1-b][1,3,4]oxadiazole-5-ol,5-aminoimidazo[5,1-b][1,3,4]oxadiazole-2-ol,imidazo[5,1-b][1,3,4]oxadiazole-2,7-diamine,imidazo[5,1-b][1,3,4]oxadiazole-2,7-diol,2-aminoimidazo[5,1-b][1,3,4]oxadiazole-7-ol, and7-aminoimidazo[5,1-b][1,3,4]oxadiazole-2-ol.
 27. The composition ofclaim 1 wherein said bicyclic 5-5 heteroaromatic compound having a ringjunction nitrogen is selected from the group consisting of compoundsaccording to the following formulas:

wherein Y is selected from the group consisting of S and O; and whereinD² and D⁶ are each independently selected from the group consisting ofamino, hydroxyl, N,N-dimethylamino, N,N-diethylamino, N-methylamino,N-ethylamino, N-(hydroxyethyl)amino, N-hydroxymethylamino,N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino, N,N-bis(hydroxypropyl)amino, N-phenyl,N-benzyl, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, phenoxy, methylthio, ethylthio, propylthio, furyl,pyrazolyl, triazolyl, oxazolyl, imidazolyl and thiadiazolyl.
 28. Thecomposition of claim 27 wherein said bicyclic 5-5 heteroaromaticcompound having a ring junction nitrogen is selected from the groupconsisting of imidazo[2,1-b][1,3,4]thiadiazole-5-amine,imidazo[2,1-b][1,3,4]thiadiazole-2,5,6-triamine,5,6-diaminoimidazo[2,1-b][1,3,4]thiadiazole-2-ol,5-aminoimidazo[2,1-b][1,3,4]thiadiazole-2,6-diol,2,5-diaminoimidazo[2,1-b][1,3,4]thiadiazole-6-ol,imidazo[2,1-b][1,3,4]oxadiazole-5-amine,imidazo[2,1-b][1,3,4]oxadiazole-2,5,6-triamine,5,6-diaminoimidazo[2,1-b][1,3,4]oxadiazole-2-ol,5-aminoimidazo[2,1-b][1,3,4]oxadiazole-2,6-diol,2,5-diaminoimidazo[2,1-b][1,3,4]oxadiazole-6-ol,imidazo[2,1-b][1,3,4]thiadiazole-2,6-diamine,imidazo[2,1-b][1,3,4]thiadiazole-2,6-diol,2-aminoimidazo[2,1-b][1,3,4]thiadiazole-6-ol,6-aminoimidazo[2,1-b][1,3,4]thiadiazole-2-ol,imidazo[2,1-b][1,3,4]oxadiazole-2,6-diamine,imidazo[2,1-b][1,3,4]oxadiazole-2,6-diol,2-aminoimidazo[2,1-b][1,3,4]oxadiazole-6-ol, and6-aminoimidazo[2,1-b][1,3,4]oxadiazole-2-ol.
 29. The composition ofclaim 1 further comprising at least one five-membered ring developerselected from the group consisting of thiophenes, pyrroles, furans,pyrazoles, imidazoles, thiazoles, oxazoles, isothiazoles, andisoxazoles.
 30. The composition of claim 29 wherein said five-memberedring developer is a pyrazole.
 31. The compositions of claim 30 whereinsaid five-membered ring developer is selected from the group consistingof 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine, and1-Hydroxyethyl-4,5-diaminopyrazole sulphate.
 32. The composition ofclaim 31 wherein said five-membered ring developer is selected from thegroup consisting of 1-methyl-1H-pyrazole-4,5-diamine;1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and2-(4,5-diamino-1H-pyrazol-1-yl)ethanol.
 33. The composition of claim 1wherein said bicyclic 5-5 heteroaromatic compound with a ring junctionnitrogen and incorporating thia or oxa heteroatoms contains anucleofugic leaving group selected from the group consisting ofchlorine, cyano, alkoxy, phenoxy, methylsulfonyoxy, pyridine, andpyridazone.
 34. The composition of claim 1 further comprising auxiliarydevelopers.
 35. The composition of claim 1 further comprising auxiliarycouplers.
 36. The composition of claim 1 further comprising direct dyes.37. The composition of claim 1 further comprising at least oneadditional component selected from the group consisting of oxidizingagents, thickeners, chelants, pH modifiers, buffering agents, andcarbonate ion source and radical scavenger systems.
 38. A method ofdyeing hair comprising the steps of (a) applying the composition ofclaim 1; and (b) rinsing hair.
 39. A kit comprising (a) the compositionof claim 1; (b) an oxidizing agent; and (c) auxiliary couplers and/orauxiliary developers.